Lubricant compositions comprising polymeric diphenylamine antioxidants

ABSTRACT

Disclosed in certain embodiments is a lubricating oil composition comprising an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I 
     
       
         
         
             
             
         
       
         
         wherein 
         R is H, C 1 -C 18  alkyl, C 2 -C 18  alkenyl, C 2 -C 18  alkynyl, —C(O)C 1 -C 18  alkyl, —C(O)aryl and R 1 , R 2 , R 3  and R 4  are each independently H or a linear or branched C 1 -C 18  alkyl, C 1 -C 18  alkoxy, C 1 -C 18  alkylamino, C 1 -C 18  dialkylamino, C 1 -C 18  alkylthio, C 2 -C 18  alkenyl, C 2 -C 18  alkynyl or C 7 -C 21  aralkyl and 
         wherein 
         the number average molecular weight (Mn) of the polymer composition is from about 350 g/mol to about 5000 g/mol.

RELATED APPLICATION

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/579,643, filed on Oct. 31, 2017, which is herein incorporated byreference in its entirety.

FIELD

This disclosure relates to engine lubricating oils with viscositycontrol and deposit control. In particular, this disclosure relates tolubricating oils, methods for improving viscosity control and depositcontrol of a lubricating oil in an engine or other mechanical componentlubricated with the lubricating oil, and methods for improving oxidativestability and deposit control, of a lubricating oil in an engine orother mechanical component lubricated with the lubricating oil. Thelubricating oils of this disclosure may be useful as passenger vehicleengine oil (PVEO) products or commercial vehicle engine oil (CVEO)products as well as industrial, aviation and marine lubricants andgreases.

BACKGROUND

Lubricant oxidative stability is one of the key parameters controllingoil life, which translates to oil drain interval in practical terms.Additionally, deposit formation is an issue associated with thedecomposition of the base stock molecules mostly propagated by oxidativechain reactions. There are several conventional approaches to improvethe resistance to oxidation of a finished lubricant product, but mostproducts are formulated using small molecules such as diphenylamine(DPA) or a phenolic antioxidant.

Improved oxidation stability is necessary to increase oil life and oildrain intervals, thus reducing the amount of used oil generated as aconsequence of more frequent oil changes. Longer oil life and oil drainintervals are key benefits that are desirable to end customers.Traditional antioxidant packages provide standard protection leaving themain differentiation hinging on the quality of the base stock in theformulation.

What is needed are newly designed lubricants capable of controllingoxidation and oil thickening for longer periods of time as compared toconventional lubricants. Further, what are needed are newly designedlubricants that enable extended oil life in combination with desireddeposit control and cleanliness performance.

SUMMARY

In certain embodiments, the present disclosure is directed to alubricating oil composition comprising a base oil and an antioxidantpolymer (e.g., oligomer) composition comprising repeat units ofdiphenylamine monomers of formula I

wherein

-   R is H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, —C(O)C₁-C₁₈    alkyl, —C(O)aryl and R₁, R₂, R₃ and R₄ are each independently H or a    linear or branched C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, C₁-C₁₈ alkylamino,    C₁-C₁₈ dialkylamino, C₁-C₁₈ alkylthio, C₂-C₁₈ alkenyl, C₂-C₁₈    alkynyl or C₇-C₂₁ aralkyl. In certain embodiments, the number    average molecular weight (Mn) of the antioxidant polymer (e.g.,    oligomer) composition is at least about 350 g/mol or from about 350    g/mol to about 5000 g/mol.

Also disclosed in certain embodiments is a lubricating oil compositioncomprising an antioxidant polymer (e.g., oligomer) compositioncomprising≤about 99 wt %, ≤about 90 wt %, ≤about 80 wt %, ≤about 70 wt%, ≤about 65 wt %, ≤about 60 wt %, ≤about 55 wt %, ≤about 50 wt %,≤about 45 wt %, ≤about 40 wt %, ≤about 35 wt %, ≤about 30 wt %, <about25 wt %, ≤about 20 wt %, ≤about 15 wt %, ≤about 10 wt %, ≤about 5 wt %,≤about 1 wt %, ≤about 0.5 wt %, ≤about 0.1 wt %, ≤about 0.05 wt % or≤about 0.01 wt % residual monomers of formula I. For example, in certainembodiments, disclosed is an antioxidant polymer (e.g., oligomer)composition comprising repeat units of diphenylamine monomers of formulaI, wherein the composition comprises from any one of about 0.01 wt %,about 0.05 wt %, about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 2wt % , about 3 wt %, about 4 wt %, about 5 wt %, about 7 wt %, about 9wt %, ab about 70 wt %out 11 wt % or about 13 wt % to any one of about15 wt %, about 18 wt %, about 21 wt %, about 24 wt %, about 27 about 70wt % wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %,about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt%, about 80 wt % or about 99 wt % residual monomers of formula I, basedon the total weight of the antioxidant composition.

In certain embodiments wherein the polymer (e.g., oligomer) compositioncomprises residual monomers, about 90 wt %, about 91 wt %, about 92 wt%, about 93 wt %, about 94 wt % or about 95 wt % to about 96 wt %, about97 wt %, about 98 wt %, about 99 wt % or 100 wt % of the residualmonomer(s) is of formula I wherein one or both of R₁ and R₄ areindependently C₄-C₁₈ alkyl, C₄-C₁₈ alkenyl or C₇-C₂₁ aralkyl, based onthe total weight of residual monomer(s).

In certain other embodiments, the disclosure is directed to a method ofextending an oil drain interval of an engine (e.g., by preventingoxidation of base stock and additives), the method comprising adding tothe engine the lubricating oil composition as disclosed herein.

Also disclosed in certain embodiments is a process of manufacturing alubricating oil composition protected against the deleterious effects ofheat and oxygen, comprising adding an antioxidant polymer (e.g.,oligomer) composition comprising repeat units of diphenylamine monomersof formula I (with or without residual monomer(s)) to a base oil.

Also disclosed are lubricating grease composition comprising a base oiland an antioxidant polymer (e.g., oligomer) composition comprisingrepeat units of diphenylamine monomers of formula I. The greasecomposition can be used in many industrial and consumer applicationssuch as lubricating a bearing such as a rolling element bearing, e g. aspherical roller bearing, a taper roller bearing, a cylindrical rollerbearing, a needle roller bearing, a ball bearing, and may also be usedto lubricate a sliding or plain bearing. The grease composition can alsobe used in coupling and gearing applications.

DETAILED DESCRIPTION

In certain embodiments, the present disclosure is directed to alubricating oil composition comprising a base oil and an antioxidantpolymer (e.g., oligomer) composition comprising repeat units ofdiphenylamine monomers of formula I

wherein R is H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,—C(O)C₁-C₁₈ alkyl, —C(O)aryl; and R₁, R₂, R₃ and R₄ are eachindependently H or a linear or branched C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,C₁-C₁₈ alkylamino, C₁-C₁₈ dialkylamino, C₁-C₁₈ alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl or C₇-C₂₁ aralkyl. In certain embodiments, thenumber average molecular weight (Mn) of the antioxidant polymer (e.g.,oligomer) composition is at least about 350 g/mol or from about 350g/mol to about 5000 g/mol.

In other embodiments, the antioxidant polymer (e.g., oligomer)compositions of the disclosure have an Mn of from about 900 g/mol orabout 1000 g/mol to about 1200 g/mol or an Mn of any one of from about400 g/mol, about 430 g/mol, about 460 g/mol, about 490 g/mol, about 520g/mol, about 550 g/mol, about 580 g/mol, about 610 g/mol, about 640g/mol, about 670 g/mol, about 700 g/mol or about 730 g/mol g/mol to anyone of about 760 g/mol, about 790 g/mol, about 820 g/mol, about 850g/mol, about 880 g/mol, about 910 g/mol, about 940 g/mol, about 970g/mol, about 1000 g/mol, about 1030 g/mol, about 1060 g/mol, about 1090g/mol, about 1120 g/mol, about 1150 g/mol, about 1180 g/mol, about 1210g/mol, about 1240 g/mol, about 1270 g/mol, about 1300 g/mol, about 1400g/mol, about 1500 g/mol, about 1600 g/mol, about 1700 g/mol, about 2000g/mol, about 2100 g/mol, about 2200 g/mol, about 2300 g/mol, about 2400g/mol, about 2500 g/mol, about 3000 g/mol, about 3500 g/mol, about 4000g/mol or about 5000 g/mol.

The number average molecular weight can be determined, for example, bygel permeation chromatography (GPC) techniques with a polystyrenestandard. GPC conditions may include testing relative to a set ofpolystyrene standards (EasiCal PS-1, low and high and PS162). Samplesare prepared in tetrahydrofuran (THF) and duplicate injections ofsolutions are run. Similar conditions may also be employed.

In certain embodiments, less than about 25 percent by weight of theantioxidant composition contains molecules having a molecular weight ofless than about 1000 g/mol.

In certain embodiments, the present disclosure is directed to alubricating oil composition comprising a base oil and an antioxidantpolymer (e.g., oligomer) composition comprising repeat units ofdiphenylamine monomers of formula II

wherein R and R′ are each independently H or a linear or branched C₁-C₁₈alkyl, C₂-C₁₈ alkenyl or C₇-C₂₁ aralkyl. In certain embodiments, R andR′ are each independently H, tert-butyl or tert-octyl.

Linear or branched alkyl includes methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl,n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl,3-methylheptyl, n-octyl, tert-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl,1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl and octadecyl. Alkyl groups mentioned herein arelinear or branched.

The alkyl portion of alkoxy, alkylamine, dialkylamino and alkylthiogroups are linear or branched and include the alkyl groups mentionedabove.

Alkenyl is an unsaturated alkyl, for instance allyl. Alkynyl includes atriple bond.

Aralkyl includes benzyl, a-methylbenzyl, a,a-dimethylbenzyl and2-phenylethyl.

Diphenylamine antioxidants are commercially available, for example underthe trade names IRGANOX L57, IRGANOX L67 and IRGANOX L01.

In certain embodiments, the antioxidant polymer (e.g., oligomer)compositions of the disclosure can be prepared by a process comprisingsubjecting diphenylamine monomers of formula I

wherein R is H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,—C(O)C₁-C₁₈ alkyl, —C(O)aryl; and R₁, R₂, R₃ and R₄ are eachindependently H or a linear or branched C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,C₁-C₁₈ alkylamino, C₁-C₁₈ dialkylamino, C₁-C₁₈ alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl or C₇-C₂₁ aralkyl to dehydrocondensationconditions.

Dehydrocondensation conditions comprise exposing monomers of formula Itooxidative conditions, for example, by exposure to a compound capable offorming free radicals. Compounds capable of forming free radicalsinclude inorganic and organic peroxides, such as di-t-butylperoxide anddi-t-amylperoxide. The dehydrocondensation reaction may be performedneat, that is, without added solvent, or may be performed in thepresence of a solvent. Suitable solvents include alkanes such as hexane,heptane, octane, nonane, decane, undecane or dodecane.Dehydrocondensation may be performed in the presence of a base stock(e.g., ester, mineral, synthetic, GTL or alkyl naphthalene base stocks).

In some embodiments, the dehydrocondensation conditions comprisereaction temperatures of any one of from about 40° C., about 60° C.,about 80° C., about 100° C., about 120° C., about 140° C. or about 160°C. to any one of about 180° C., about 200° C., about 220° C., about 240°C. or about 250° C.

In certain embodiments, the dehydrocondensation conditions comprise areaction time of any one of from about 0.3 hours, about 0.5 hour, about1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours orabout 6 hours to any one of about 7 hours, about 8 hours, about 9 hours,about 10 hours, about 11 hours or about 12 hours. In other embodiments,the dehydrocondensation conditions may comprise a reaction time of fromany one of about 12 hours, about 24 hours, about 36 hours, about 48hours or about 60 hours to any one of about 72 hours, about 84 hours,about 96 hours, about 108 hours or about 120 hours.

The oxidative conditions remove hydrogen from the monomers, whichsubsequently couple through C—N, C—C or N—N bonds. When an alkanesolvent is used, the solvent appears to be inert and to not be involvedin the reaction. Therefore, the produced polymer (e.g., oligomer) maycontain no alkane solvent fragments.

The term “oligomer comprising repeat units of diphenylamine monomers”means the oligomers contain “reacted in” monomers, that is, radicals ofmonomers.

In certain embodiments, the lubricating oil compositions of the presentdisclosure provide for an improvement in at least one of viscositycontrol and deposits prevention as compared to a lubricating oilcomposition that does not contain the oligomer compositions of thepresent disclosure.

Viscosity control and deposit prevention may be determined by industrystandard tests, for instance a TEOST MHT 4 test (ASTM D7097) bench testor Sequence IITH Test (ASTM D8111) engine test. Tests may be modified toincrease the severity, for example by increasing temperature and/or timeof a test.

In some embodiments, the lubricating oil compositions of the presentdisclosure exhibits color according to ASTM D1500 of any one of about3.5, about 4.0, about 4.5, about 5.0, about 5.5 or about 6.0. In certainembodiments, the lubricating oil compositions exhibit color according toASTM D1500 of <6.0. In certain embodiments, the lubricating oilcompositions of the present disclosure exhibit a lower color accordingto ASTM D1500 relative to compositions containing other polymeric aminicantioxidants, for example relative to compositions containing polymericphenylnaphthylamine antioxidants.

The antioxidant polymer (e.g., oligomer) compositions of the presentdisclosure may contain a mixture of different chain lengths. Forexample, the composition may contain residual unreacted monomer as wellas fragments or chains having molecular weights above or below theranges mentioned above. Residual monomer means unreacted monomer. Thepolymer (e.g., oligomer) may be purified, for example by a stepcomprising chromatography or distillation. In one embodiment, theproduced polymer (e.g., oligomer) composition may be subject to reducedpressure to remove residual monomer.

Accordingly, the polymer (e.g., oligomer) composition of the presentdisclosure may contain ≤about 99 wt %, ≤about 90 wt %, ≤about 80 wt %,≤about 70 wt %, ≤about 65 wt %, ≤about 60 wt %, ≤about 55 wt %, ≤about50 wt %, ≤about 45 wt %, ≤about 40 wt %, ≤about 35 wt %, ≤about 30 wt %,≤about 25 wt %, ≤about 20 wt %, ≤about 15 wt %, ≤about 10 wt % ≤about 5wt %, ≤about 1 wt %, ≤about 0.5 wt %, ≤about 0.1 wt %, ≤about 0.05 wt %or ≤about 0.01 wt % residual monomers of formula I, based on the weightof the composition. For example, in certain embodiments, disclosed is apolymer (e.g., oligomer) composition comprising repeat units ofdiphenylamine monomers of formula I, wherein the composition comprisesfrom any one of about 0.01 wt %, about 0.05 wt %, about 0.1 wt %, about0.5 wt %, about 1 wt %, about 2 wt % , about 3 wt %, about 4 wt %, about5 wt %, about 7 wt %, about 9 wt %, about 11 wt % or about 13 wt % toany one of about 15 wt %, about 18 wt %, about 21 wt %, about 24 wt %,about 27 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt%, about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt % about 70wt %, about 80 wt % or about 99 wt % residual monomers of formula I,based on the total weight of the antioxidant composition.

In certain embodiments, the purification steps to remove residualmonomers include subjecting the polymer (e.g., oligomer) composition toreduced pressure. In certain embodiments, the remaining monomer in thecomposition will include higher molecular weight monomers, e.g., di- ortri-alkyl substituted monomers. In some embodiments, wherein the polymer(e.g., oligomer) composition contains residual monomer, any one of fromabout 90 wt %, about 91 wt %, about 92 wt %, about 93 wt %, about 94 wt% or about 95 wt % to any one of about 96 wt %, about 97, about 98,about 99 or 100 wt % of the residual monomer is of formula I wherein R₁and R₄ are independently C₄-C₁₈ alkyl, C₄-C₁₈ alkenyl or C₇-C₂₁ aralkyl,based on the total weight of residual monomer.

In certain embodiments, the polymer (e.g., oligomer) composition mayalso be characterized by its viscosity. For example, the present polymer(e.g., oligomer) compositions of the disclosure may have a kinematicviscosity at 100° C. of from any one of about 10 cSt to about 2,500 cSt.In other embodiments, the kinematic viscosity at 100° C. may be from anyone of about 10 cSt, about 20 cSt, about 30 cSt, about 40 cSt, about 50cSt, about 60 cSt, about 70 cSt, about 80 cSt, about 81 cSt, about 82cSt, about 83 cSt, about 84 cSt, about 85 cSt, about 86 cSt, about 87cSt, about 88 cSt, about 89 cSt, about 90 cSt, about 91 cSt, about 92cSt, about 93 cSt, about 94 cSt, about 95 cSt, about 96 cSt, about 97cSt, about 98 cSt or about 99 cSt to any one of about 100 cSt, about 101cSt, about 102 cSt, about 103 cSt, about 104 cSt, about 105 cSt, about106 cSt, about 107 cSt, about 108 cSt, about 109 cSt, about 110 cSt,about 111 cSt, about 112 cSt, about 113 cSt, about 114 cSt, about 115cSt, about 116 cSt, about 117 cSt, about 118 cSt, about 119 cSt , about120 cSt, about 500 cSt, about 1,000 cSt, about 1,500 cSt, about 2,000cSt or about 2,500 cSt.

In certain other embodiments of the disclosure, the antioxidant polymer(e.g., oligomer) compositions may have a kinematic viscosity 100° C. offrom any one of about 120 cSt, about 140 cSt, about 170 cSt, about 190cSt, about 210 cSt, about 230 cSt, about 260 cSt, about 310 cSt or about360 cSt to any one of about 400 cSt, about 420 cSt, about 450 cSt, about470 cSt, about 500 cSt, about 530 cSt, about 570 cSt or about 600 cSt.In certain other embodiments, the polymer (e.g., oligomer) compositionsmay be solids.

Viscosity may be determined according to ASTM D445 or equivalent orsimilar methods measured at 100° C.

In certain embodiments, further monomers may be included in thepolymerization reaction. For example, present polymer (e.g., oligomer)smay contain one or more monomers selected from the group consisting ofother diphenylamines, phenothiazines, phenoxazines, aminodiphenylamines,methylenedianiline, toluenediamine, aminophenols, alkylphenols,thiophenols, phenylenediamines, quinolines, phenyl pyridinediamines,pyridinepyrimidinediamines, naphthylphenylamines andphenylpyrimidinediamines.

In some embodiments, present polymer (e.g., oligomer) compositionscomprise any one of from about 1 mol %, 10 mol %, about 20 mol %, about30 mol %, about 40 mol % or about 50 mol % to any one of about 60 mol %,about 70 mol %, about 80 mol %, about 90 mol %, about 95 mol %, about 96mol %, about 97 mol %, about 98 mol %, about 99 mol % or 100 mol %diphenylamine monomers of formula I.

In certain embodiments, the polymeric compositions disclosed herein areoligomeric compositions (i.e., dimers, trimers and tetramers).

In certain embodiments, the polymeric compositions disclosed hereincomprise one or more of dimers, trimers, tetramers or higher repeatingunits (i.e. a polymer of 5 or more monomers).

In certain embodiments, the polymeric compositions have an amount ofdimers that are greater than the amount of higher repeating units.

In certain embodiments, the polymeric compositions have an amount oftrimers that are greater than the amount of higher repeating units.

In certain embodiments, the polymeric compositions have a combinedamount of dimers and trimers that are greater than the amount of higherrepeating units.

In certain embodiments, the polymeric compositions have at least 75% Mnof greater than 1000. In other embodiments, the polymeric compositionshave about 20% to about 80%, about 25% to about 75%, about 30% to about70% or about 40% to about 60% Mn of greater than 1000.

In certain embodiments, the polymeric compositions have at least 75% Mnof less than 1000. In other embodiments, the polymeric compositions haveabout 10% to about 100%, about 20% to about 80%, about 25% to about 75%,about 30% to about 70% or about 40% to about 60% Mn of less than 1000.

In certain embodiments, the polymeric compositions have an amount ofdimers of from any one of about 5%, about 10%, about 15%, about 20%,about 25% or about 30% to any one of about 40%, about 45%, about 50%,about 55%, about 60%, about 70%, about 80%, about 90% or about 100%. Incertain embodiments, the dimers have a number average molecular weight(Mn) of about 300 to about 850.

In certain embodiments, the polymeric compositions have an amount oftrimers of from any one of about 10%, about 15%, about 20%, about 25%,about 30% or about 40% to any one of about 50%, about 55%, about 60%,about 65%, about 70%, about 80%, about 90% or about 100%. In certainembodiments, the trimers have a number average molecular weight (Mn) ofabout 400 to about 1200.

In certain embodiments, the polymeric compositions have an amount oftetramers of from any one of about 15%, about 20%, about 25%, about 30%,about 40% or about 50% to any one of about 55%, about 60%, about 65%,about 70%, about 75%, about 80%, about 90% or about 100%. In certainembodiments, the tetramers have a number average molecular weight (Mn)of about 500 to about 1500.

In certain embodiments, the polymeric compositions have an amount ofhigher repeating units of from any one of about 5%, about 10%, about25%, about 30%, about 40% to any one of about 50%, about 60%, about 70%,about 80%, about 90% or about 100%. In certain embodiments, the higherrepeating units have a number average molecular weight (Mn) of greaterthan about 1000 or greater than about 1174.

In certain embodiments polymeric composition have m/z ions ranging from300 to 1000. In certain embodiments, the above m/z ions include 838Daltons, 894 Daltons or 911 Daltons.

In certain embodiments, the polymeric compositions have an m/z ion countfrom about 300 to about 1,000 of greater than about 50, greater thanabout 75, greater than about 100, greater than about 150, greater thanabout 200, greater than about 250, greater than about 300 or greaterthan about 350. In certain embodiments, the polymeric compositions havean m/z ion count from about 800 to about 1,000 of from any one of about50, about 75, about 100 or about 150 to any one of about 200, about 250,about 300 or about 350.

In certain embodiments, the polymeric compositions exhibit a VIT(h) ofgreater than about 600, greater than about 650, greater than about 700,or greater than about 850. In certain embodiments, the polymericcompositions exhibit a VIT(h) of from any one of about 600, about 650,or about 700 to any one of about 900, about 1,200 or about 1,500. Acomparator monomer composition provides a VIT(h) of 472. The VIT test isperformed by placing a sample of formulated oil in a glass tube with ahomogeneous catalyst consisting of iron, copper and lead. Air is bubbledthrough the sample at a rate of 8L/h and heated to 150 ° C. Thekinematic viscosity (KV40) is monitored throughout the test, and thedata fit to a power curve to calculate the time, in hours, it takes forthe sample to reach 150% of its original KV40.

In certain embodiments, disclosed is a grease formulation that providesa value of greater than 100, greater than 110 or greater than 120 whentested according to DIN 51821 FAG FE9 AFAG FE9 A/1500/6000 @140 C (B50,hours) when the grease formulation comprises 1% of the disclosed polymercomposition.

In certain embodiments, disclosed is an industrial oil formulation thatprovides a value of greater than 2000, greater than 2025 or greater than2050 when tested according to ASTM D2272-RPVOT at 150 C (min) when theindustrial oil formulation comprises 1% of the disclosed polymercomposition.

In certain embodiments, disclosed is an industrial oil formulation thatprovides a value of greater than 2100, greater than 2200 or greater than2500 when tested according to ASTM D2272-RPVOT at 150C (min) when theindustrial oil formulation comprises 0.7% of the disclosed polymercomposition.

In certain embodiments, disclosed is an industrial oil formulation thatprovides a value of greater than 225, greater than 230 or greater than235 when tested according to High Pressure Differential Scanningcalorimetry (min) when the industrial oil formulation comprises 1% ofthe disclosed polymer composition.

In certain embodiments, disclosed is an industrial oil formulation thatprovides a value of greater than 50, greater than 65 or greater than 80when tested according to High Pressure Differential Scanning calorimetry(min) when the industrial oil formulation comprises 0.7% of thedisclosed polymer composition.

In certain embodiments, disclosed is a passenger vehicle lubricantformulation that provides a value of less than 52, less than 46 or lessthan 40 when tested according to ASTM D7097-TEOST MHT4 (Total deposits,mg) when the passenger vehicle lubricant formulation comprises 2% of thedisclosed polymer composition.

In certain embodiments, disclosed is a passenger vehicle lubricantformulation that provides a value of less than 35, less than 34 or lessthan 32 when tested according to ASTM D6335-TEOST 33 C (Total deposits,mg) when the passenger vehicle lubricant formulation comprises 2% of thedisclosed polymer composition.

In certain embodiments, disclosed is a passenger vehicle lubricantformulation that provides a value of less than 400, less than 300, lessthan 200, less than 150 or less than 75 when tested according to ASTMD8111-Sequence IIIH, EOT % Viscosity increase when the passenger vehiclelubricant formulation comprises 2% of the disclosed polymer composition.

In certain embodiments, disclosed is a passenger vehicle lubricantformulation that provides a value of greater than 4.8, greater than 4.9,greater than 5.0 or greater than 5.1 when tested according to ASTMD8111-Sequence IIIH, Weighted Piston Deposit Merits when the passengervehicle lubricant formulation comprises 2% of the disclosed polymercomposition.

In certain embodiments, disclosed is a passenger vehicle lubricantformulation that provides a value of greater than 9.7, greater than 9.75or greater than 9.8 when tested according to ASTM D8111-Sequence IIIH,Average Piston Varnish Merits when the passenger vehicle lubricantformulation comprises 2% of the disclosed polymer composition.

In certain embodiments, disclosed is a commercial vehicle lubricantformulation that provides a value of less than 145, less than 135 orless than 125 when tested according to ASTM D8048-Volvo T-13, IR PeakIncrease when the commercial vehicle lubricant formulation comprises1.4% of the disclosed polymer composition.

The lubricating oil formulations of the present disclosure include butare not limited to greases, gear oils, hydraulic oils, brake fluids,manual and automatic transmission fluids, other energy transferringfluids, tractor fluids, diesel compression ignition engine oils,gasoline spark ignition engine oils, turbine oils and the like. Thelubricating base oil may be selected from the group consisting ofnatural oils, petroleum-derived mineral oils, synthetic oils andmixtures thereof. The lubricant to include in the disclosed formulationsmay be referred to as a “base fluid”, “base oil”, “lubricating oil” or“lubricant”.

A wide range of lubricating base oils is known in the art. Lubricatingbase oils that may be useful in the present disclosure are both naturaloils, and synthetic oils, and unconventional oils (or mixtures thereof)can be used unrefined, refined, or rerefined (the latter is also knownas reclaimed or reprocessed oil). Unrefined oils are those obtaineddirectly from a natural or synthetic source and used without addedpurification. These include shale oil obtained directly from retortingoperations, petroleum oil obtained directly from primary distillation,and ester oil obtained directly from an esterification process. Refinedoils are similar to the oils discussed for unrefined oils except refinedoils are subjected to one or more purification steps to improve at leastone lubricating oil property. One skilled in the art is familiar withmany purification processes. These processes include solvent extraction,secondary distillation, acid extraction, base extraction, filtration,and percolation. Rerefined oils are obtained by processes analogous torefined oils but using an oil that has been previously used as a feedstock.

Groups I, II, III, IV and V are broad base oil stock categoriesdeveloped and defined by the American Petroleum Institute (APIPublication 1509; www.API.org to create guidelines for lubricant baseoils. Group I base stocks have a viscosity index of from 80 to 120 andcontain greater than 0.03% sulfur and/or less than 90% saturates. GroupII base stocks have a viscosity index of from 80 to 120, and containless than or equal to 0.03% sulfur and greater than or equal to 90%saturates. Group III stocks have a viscosity index greater than 120 andcontain less than or equal to 0.03% sulfur and greater than 90%saturates. Group IV includes polyalphaolefins (PAO). Group V base stockincludes base stocks not included in Groups I-IV. The table belowsummarizes properties of each of these five groups.

saturates sulfur viscosity index Group I  <90 and/or  >0.03% and ≥80 and<120 Group II ≥90 and ≤0.03% and ≥80 and <120 Group III ≥90 and ≤0.03%and ≥120 Group IV ---- polyalphaolefins (PAO) ---- Group V --- all otherbase stocks not of Groups I-IV ----

Natural oils include animal oils, vegetable oils (castor oil and lardoil, for example), and mineral oils. Animal and vegetable oilspossessing favorable thermal oxidative stability can be used. Of thenatural oils, mineral oils are preferred. Mineral oils vary widely as totheir crude source, for example, as to whether they are paraffinic,naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal orshale are also useful. Natural oils vary also as to the method used fortheir production and purification, for example, their distillation rangeand whether they are straight run or cracked, hydrorefined, or solventextracted.

Group II and/or Group III hydroprocessed or hydrocracked base stocks,including synthetic oils such as polyalphaolefins, alkyl aromatics andsynthetic esters are also well known base stock oils.

Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oilssuch as polymerized and interpolymerized olefins (polybutylenes,polypropylenes, propylene isobutylene copolymers, ethylene-olefincopolymers, and ethylene-alphaolefin copolymers, for example).Polyalphaolefin (PAO) oil base stocks are commonly used synthetichydrocarbon oil. By way of example, PAOs derived from C₆, C₈, C₁₀, C₁₂,C₁₄ olefins or mixtures thereof may be utilized. See U.S. Pat. Nos.4,956,122; 4,827,064; and 4,827,073.

The number average molecular weights of the PAOs, which are knownmaterials and generally available on a major commercial scale fromsuppliers such as ExxonMobil Chemical Company, Chevron Phillips ChemicalCompany, BP, and others, typically vary from 250 to 3,000, althoughPAO's may be made in viscosities up to 100 cSt (100° C.). The PAOs aretypically comprised of relatively low molecular weight hydrogenatedpolymers or oligomers of alphaolefins which include, but are not limitedto, C₂ to C₃₂ alphaolefins with the C₈ to C₁₆ alphaolefins, such as1-hexene, 1-octene, 1-decene, 1-dodecene and the like, being preferred.The preferred polyalphaolefins are poly-1-hexene, poly-1-octene,poly-l-decene and poly-1-dodecene and mixtures thereof and mixedolefin-derived polyolefins. However, the dimers of higher olefins in therange of C₁₄ to C₁₈ may be used to provide low viscosity base stocks ofacceptably low volatility. Depending on the viscosity grade and thestarting polymer (e.g., oligomer), the PAOs may be predominantly trimersand tetramers of the starting olefins, with minor amounts of the higherpolymers, having a viscosity range of 1.5 to 12 cSt. PAO fluids ofparticular use may include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt andcombinations thereof. Bi-modal mixtures of PAO fluids having a viscosityrange of 1.5 to about 100 cSt or to about 300 cSt may be used ifdesired.

The PAO fluids may be conveniently made by the polymerization of analphaolefin in the presence of a polymerization catalyst such as theFriedel-Crafts catalysts including, for example, aluminum trichloride,boron trifluoride or complexes of boron trifluoride with water, alcoholssuch as ethanol, propanol or butanol, carboxylic acids or esters such asethyl acetate or ethyl propionate. For example the methods disclosed byU.S. Pat. No. 4,149,178 or 3,382,291 may be conveniently used herein.Other descriptions of PAO synthesis are found in the following U.S. Pat.Nos. 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413,156;4,434,408; 4,910,355; 4,956,122; and 5,068,487. The dimers of the C₁₄ toC₁₈ olefins are described in U.S. Pat. No. 4,218,330.

Other useful lubricant oil base stocks include wax isomerate base stocksand base oils, comprising hydroisomerized waxy stocks (e.g. waxy stockssuch as gas oils, slack waxes, fuels hydrocracker bottoms, etc.),hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocksand base oils, and other wax isomerate hydroisomerized base stocks andbase oils, or mixtures thereof Fischer-Tropsch waxes, the high boilingpoint residues of Fischer-Tropsch synthesis, are highly paraffinichydrocarbons with very low sulfur content. The hydroprocessing used forthe production of such base stocks may use an amorphoushydrocracking/hydroisomerization catalyst, such as one of thespecialized lube hydrocracking (LHDC) catalysts or a crystallinehydrocracking/hydroisomerization catalyst, preferably a zeoliticcatalyst. For example, one useful catalyst is ZSM-48 as described inU.S. Pat. No. 5,075,269, the disclosure of which is incorporated hereinby reference in its entirety. Processes for makinghydrocracked/hydroisomerized distillates andhydrocracked/hydroisomerized waxes are described, for example, in U.S.Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as well as inBritish Patent Nos. 1,429,494; 1,350,257; 1,440,230 and 1,390,359. Eachof the aforementioned patents is incorporated herein in their entirety.Particularly favorable processes are described in European PatentApplication Nos. 464546 and 464547, also incorporated herein byreference. Processes using Fischer-Tropsch wax feeds are described inU.S. Pat. Nos. 4,594,172 and 4,943,672, the disclosures of which areincorporated herein by reference in their entirety.

Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils,and other wax-derived hydroisomerized (wax isomerate) base oils beadvantageously used in the instant disclosure, and may have usefulkinematic viscosities at 100° C. of 3 cSt to 50 cSt, preferably 3 cSt to30 cSt, more preferably 3.5 cSt to 25 cSt, as exemplified by GTL 4 withkinematic viscosity of 4.0 cSt at 100° C. and a viscosity index of 141.These Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived baseoils, and other wax-derived hydroisomerized base oils may have usefulpour points of −20° C. or lower, and under some conditions may haveadvantageous pour points of −25° C. or lower, with useful pour points of−30° C. to −40° C. or lower. Useful compositions of Gas-to-Liquids (GTL)base oils, Fischer-Tropsch wax derived base oils, and wax-derivedhydroisomerized base oils are recited in U.S. Pat. Nos. 6,080,301;6,090,989, and 6,165,949 for example, and are incorporated herein intheir entirety by reference.

The hydrocarbyl aromatics can be used as base oil or base oil componentand can be any hydrocarbyl molecule that contains at least 5% of itsweight derived from an aromatic moiety such as a benzenoid moiety ornaphthenoid moiety, or their derivatives. These hydrocarbyl aromaticsinclude alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkylnaphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylatedthiodiphenol, and the like. The aromatic can be mono-alkylated,dialkylated, polyalkylated, and the like. The aromatic can be mono- orpoly-functionalized. The hydrocarbyl groups can also be comprised ofmixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups,cycloalkenyl groups and other related hydrocarbyl groups. Thehydrocarbyl groups can range from C₆ up to C₆₀ with a range of C₈ to C₂₀often being preferred. A mixture of hydrocarbyl groups is oftenpreferred, and up to three such substituents may be present.

The hydrocarbyl group can optionally contain sulfur, oxygen, and/ornitrogen containing substituents. The aromatic group can also be derivedfrom natural (petroleum) sources, provided at least 5% of the moleculeis comprised of an above-type aromatic moiety. Viscosities at 100° C. ofabout 3 cSt to about 50 cSt are preferred, with viscosities of about 3.4cSt to about 20 cSt often being more preferred for the hydrocarbylaromatic component. In one embodiment, an alkyl naphthalene where thealkyl group is primarily comprised of 1-hexadecene is used. Otheralkylates of aromatics can be advantageously used. Naphthalene or methylnaphthalene, for example, can be alkylated with olefins such as octene,decene, dodecene, tetradecene or higher, mixtures of similar olefins,and the like. Useful concentrations of hydrocarbyl aromatic in alubricant oil composition can be 2% to 25%, preferably 4% to 20%, andmore preferably 4% to 15%, depending on the application.

Alkylated aromatics such as the hydrocarbyl aromatics of the presentdisclosure may be produced by well-known Friedel-Crafts alkylation ofaromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G.A. (ed.), Inter-science Publishers, New York, 1963. For example, anaromatic compound, such as benzene or naphthalene, is alkylated by anolefin, alkyl halide or alcohol in the presence of a Friedel-Craftscatalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1,chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-sciencePublishers, New York, 1964. Many homogeneous or heterogeneous, solidcatalysts are known to one skilled in the art. The choice of catalystdepends on the reactivity of the starting materials and product qualityrequirements. For example, strong acids such as AlCl₃, BF3, or HF may beused. In some cases, milder catalysts such as FeCl₃ or SnCl₄ arepreferred. Newer alkylation technology uses zeolites or solid superacids.

Esters comprise a useful base stock. Additive solvency and sealcompatibility characteristics may be secured by the use of esters suchas the esters of dibasic acids with monoalkanols and the polyol estersof monocarboxylic acids. Esters of the former type include, for example,the esters of dicarboxylic acids such as phthalic acid, succinic acid,alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid,suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.,with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, etc. Specific examples of these types ofesters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexylfumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.

Particularly useful synthetic esters may be those which are obtained byreacting one or more polyhydric alcohols, preferably the hinderedpolyols (such as the neopentyl polyols, e.g., neopentyl glycol,trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, trimethylolpropane, pentaerythritol and dipentaerythritol) with alkanoic acidscontaining at least 4 carbon atoms, preferably C₅ to C₃₀ acids such assaturated straight chain fatty acids including caprylic acid, capricacid, lauric acid, myristic acid, palmitic acid, stearic acid, arachicacid, and behenic acid, or the corresponding branched chain fatty acidsor unsaturated fatty acids such as oleic acid, or mixtures of any ofthese materials.

Suitable synthetic ester components include the esters of trimethylolpropane, trimethylol butane, trimethylol ethane, pentaerythritol and/ordipentaerythritol with one or more monocarboxylic acids containing from5 to 10 carbon atoms. These esters are widely available commercially,for example, the Mobil P-41 and P-51 esters of ExxonMobil ChemicalCompany.

Also useful are esters derived from renewable material such as coconut,palm, rapeseed, soy, sunflower and the like. These esters may bemonoesters, di-esters, polyol esters, complex esters, or mixturesthereof. These esters are widely available commercially, for example,the Mobil P-51 ester of ExxonMobil Chemical Company.

Engine oil formulations containing renewable esters are included in thisdisclosure. For such formulations, the renewable content of the ester istypically greater than 70 weight percent, preferably more than 80 weightpercent and most preferably more than 90 weight percent. Renewableesters can be preferred in combination with the friction modifiermixture.

Other useful fluids of lubricating viscosity include non-conventional orunconventional base stocks that have been processed, preferablycatalytically, or synthesized to provide high performance lubricationcharacteristics.

Non-conventional or unconventional base stocks/base oils include one ormore of a mixture of base stock(s) derived from one or moreGas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate basestock(s) derived from natural wax or waxy feeds, mineral and ornon-mineral oil waxy feed stocks such as slack waxes, natural waxes, andwaxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxyraffinate, hydrocrackate, thermal crackates, or other mineral, mineraloil, or even non-petroleum oil derived waxy materials such as waxymaterials received from coal liquefaction or shale oil, and mixtures ofsuch base stocks.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds and/or elements as feed stockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and/or base oils are GTLmaterials of lubricating viscosity that are generally derived fromhydrocarbons; for example, waxy synthesized hydrocarbons, that arethemselves derived from simpler gaseous carbon-containing compounds,hydrogen-containing compounds and/or elements as feed stocks. GTL basestock(s) and/or base oil(s) include oils boiling in the lube oil boilingrange (1) separated/fractionated from synthesized GTL materials such as,for example, by distillation and subsequently subjected to a final waxprocessing step which involves either or both of a catalytic dewaxingprocess, or a solvent dewaxing process, to produce lube oils ofreduced/low pour point; (2) synthesized wax isomerates, comprising, forexample, hydrodewaxed or hydroisomerized cat and/or solvent dewaxedsynthesized wax or waxy hydrocarbons; (3) hydrodewaxed orhydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T)material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibleanalogous oxygenates); preferably hydrodewaxed orhydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxyhydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (orsolvent) dewaxing dewaxed, F-T waxes, or mixtures thereof.

GTL base stock(s) and/or base oil(s) derived from GTL materials,especially, hydrodewaxed or hydroisomerized/followed by cat and/orsolvent dewaxed wax or waxy feed, preferably F-T material derived basestock(s) and/or base oil(s), are characterized typically as havingkinematic viscosities at 100° C. of from 2 mm²/s to 50 mm²/s (ASTMD445). They are further characterized typically as having pour points of−5° C. to −40° C. or lower (ASTM D97). They are also characterizedtypically as having viscosity indices of 80 to 140 or greater (ASTMD2270).

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s)typically have very low sulfur and nitrogen content, generallycontaining less than 10 ppm, and more typically less than 5 ppm of eachof these elements. The sulfur and nitrogen content of GTL base stock(s)and/or base oil(s) obtained from F-T material, especially F-T wax, isessentially nil. In addition, the absence of phosphorous and aromaticsmake this materially especially suitable for the formulation of low SAPproducts.

The term GTL base stock and/or base oil and/or wax isomerate base stockand/or base oil is to be understood as embracing individual fractions ofsuch materials of wide viscosity range as recovered in the productionprocess, mixtures of two or more of such fractions, as well as mixturesof one or two or more low viscosity fractions with one, two or morehigher viscosity fractions to produce a blend wherein the blend exhibitsa target kinematic viscosity.

The GTL material, from which the GTL base stock(s) and/or base oil(s)is/are derived is preferably an F-T material (i.e., hydrocarbons, waxyhydrocarbons, wax).

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s) andhydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed basestock(s) and/or base oil(s) typically have very low sulfur and nitrogencontent, generally containing less than 10 ppm, and more typically lessthan 5 ppm of each of these elements. The sulfur and nitrogen content ofGTL base stock(s) and/or base oil(s) obtained from F-T material,especially F-T wax, is essentially nil. In addition, the absence ofphosphorous and aromatics make this material especially suitable for theformulation of low sulfur, sulfated ash, and phosphorus (low SAP)products.

Base oils for use in the formulated lubricating oils useful in thepresent disclosure are any of the variety of oils corresponding to APIGroup I, Group II, Group III, Group IV, and Group V oils and mixturesthereof, preferably API Group II, Group III, Group IV, and Group V oilsand mixtures thereof, more preferably the Group III to Group V base oilsdue to their exceptional volatility, stability, viscometric andcleanliness features. Minor quantities of Group I stock, such as theamount used to dilute additives for blending into formulated lube oilproducts, can be tolerated but should be kept to a minimum, i.e. amountsonly associated with their use as diluent/carrier oil for additives usedon an “as-received” basis. Even in regard to the Group II stocks, it ispreferred that the Group II stock be in the higher quality rangeassociated with that stock, i.e. a Group II stock having a viscosityindex in the range 100<VI<120.

The lubricating base oil or base stock constitutes the major componentof the engine oil lubricant composition of the present disclosure. Oneparticularly preferred lubricating oil base stock for the inventivelubricating engine oil and the inventive method for improving fuelefficiency, frictional properties and deposit control is a Group I basestock that is included in the formulated oil at from 75 to 95 wt %, orfrom 80 to 90 wt %, or from 82 to 88 wt %. Another particularlypreferred lubricating oil base stock for the inventive lubricatingengine oil and the inventive method for improving fuel efficiency,frictional properties and deposit control is a combination of a GroupIII, Group IV and Group V base stock wherein the combination is includedin the formulated oil at from 75 to 95 wt %, or from 80 to 90 wt %, orfrom 82 to 88 wt %. In this form, the Group III base stock is includedat from 30 to 35 wt % or from 32 to 33 wt %, the Group IV base stock atfrom 45 to 55 wt % or from 48 to 52 wt %, and the Group V base stock atfrom 0 to 5 wt %, or from 2 to 4 wt %.

Preferred Group III base stocks are GTL and Yubase Plus (hydroprocessedbase stock). Preferred Group V base stocks include alkylatednaphthalene, synthetic esters and combinations thereof.

In some embodiments, the base oils or base stocks described above have akinematic viscosity, according to ASTM standards, of about 2.5 cSt toabout 12 cSt (or mm²/s) at 100° C., preferably of about 2.5 cSt to about9 cSt (or mm²/s) at 100° C., more preferably of about 4 cSt to about 8cSt (or mm²/s) at 100° C., and even more preferably of about 4 cSt toabout 6 cSt (or mm²/s) at 100° C. In other embodiments, base stocks mayhave a kinematic viscosity of up to about 100 cSt, about 150 cSt, about200 cSt, about 250 cSt or about 300 cSt at 100° C.

Lubricating oils and base stocks are disclosed for example In US. Pub.Nos. 20170211007, 20150344805 and 2015322367.

The lubricating oils of the disclosure may contain one or more furtheradditives. Further additives may be present, in each case, from about0.01 wt %, about 0.1, about 0.5 or about 1 wt % to about 2 wt %, about5, about 7, about 8, about 10, about 14, about 17, about 20, about 22 orabout 25 wt %, based on the total weight of the lubricating oilformulation.

The formulated lubricating oil useful in the present disclosure mayadditionally contain one or more of the other commonly used lubricatingoil performance additives including but not limited to antiwear agents,dispersants, other detergents, corrosion inhibitors, rust inhibitors,metal deactivators, extreme pressure additives, anti-seizure agents, waxmodifiers, viscosity index improvers, viscosity modifiers, fluid-lossadditives, seal compatibility agents, organic metallic frictionmodifiers, lubricity agents, anti-staining agents, chromophoric agents,defoamants, demulsifiers, emulsifiers, densifiers, wetting agents,gelling agents, tackiness agents, colorants, and others. For a review ofmany commonly used additives, see Klamann in Lubricants and RelatedProducts, Verlag Chemie, Deerfield Beach, Fla.; ISBN 0-89573-177-0.

Reference is also made to “Lubricant Additives” by M. W. Ranney,published by Noyes Data Corporation of Parkridge, N.J. (1973); see alsoU.S. Pat. No. 7,704,930, the disclosure of which is incorporated hereinin its entirety. These additives are commonly delivered with varyingamounts of diluent oil that may range from 5 weight percent to 50 weightpercent.

The types and quantities of performance additives used in combinationwith the instant disclosure in lubricant compositions are not limited bythe examples shown herein as illustrations.

Antiwear Additives

A metal alkylthiophosphate and more particularly a metal dialkyl dithiophosphate in which the metal constituent is zinc, or zinc dialkyl dithiophosphate (ZDDP) is a useful component of the lubricating oils of thisdisclosure. ZDDP can be derived from primary alcohols, secondaryalcohols or mixtures thereof. ZDDP compounds generally are of theformula Zn[SP(S)(OR¹)(OR²)]₂ where R¹ and R² are C₁-C₁₈ alkyl groups,preferably C₂-C₁₂ alkyl groups. These alkyl groups may be straight chainor branched. Alcohols used in the ZDDP can be 2-propanol, butanol,secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol,n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like.Mixtures of secondary alcohols or of primary and secondary alcohol canbe preferred. Alkyl aryl groups may also be used.

Preferable zinc dithiophosphates which are commercially availableinclude secondary zinc dithiophosphates such as those available from forexample, The Lubrizol Corporation under the trade designations “LZ677A”, “LZ 1095” and “LZ 1371”, from for example Chevron Oronite underthe trade designation “OLOA 262” and from for example Afton Chemicalunder the trade designation “HiTEC 7169”.

The ZDDP is typically used in amounts of from 0.4 weight percent to 1.2weight percent, preferably from 0.5 weight percent to 1.0 weightpercent, and more preferably from 0.6 weight percent to 0.8 weightpercent, based on the total weight of the lubricating oil, although moreor less can often be used advantageously. Preferably, the ZDDP is asecondary ZDDP and present in an amount of from 0.6 to 1.0 weightpercent of the total weight of the lubricating oil.

Low phosphorus engine oil formulations are included in this disclosure.For such formulations, the phosphorus content is typically less than0.12 weight percent preferably less than 0.10 weight percent and mostpreferably less than 0.085 weight percent. Low phosphorus can bepreferred in combination with the friction modifier mixture.

Viscosity Index Improvers

Viscosity index improvers (also known as VI improvers, viscositymodifiers, and viscosity improvers) can be included in the lubricantcompositions of this disclosure.

Viscosity index improvers provide lubricants with high and lowtemperature operability. These additives impart shear stability atelevated temperatures and acceptable viscosity at low temperatures.

Suitable viscosity index improvers include high molecular weighthydrocarbons, polyesters and viscosity index improver dispersants thatfunction as both a viscosity index improver and a dispersant. Typicalmolecular weights of these polymers are between 10,000 to 1,500,000,more typically 20,000 to 1,200,000, and even more typically between50,000 and 1,000,000.

Examples of suitable viscosity index improvers are linear or star-shapedpolymers and copolymers of methacrylate, butadiene, olefins, oralkylated styrenes. Polyisobutylene is a commonly used viscosity indeximprover. Another suitable viscosity index improver is polymethacrylate(copolymers of various chain length alkyl methacrylates, for example),some formulations of which also serve as pour point depressants. Othersuitable viscosity index improvers include copolymers of ethylene andpropylene, hydrogenated block copolymers of styrene and isoprene, andpolyacrylates (copolymers of various chain length acrylates, forexample). Specific examples include styrene-isoprene orstyrene-butadiene based polymers of 50,000 to 200,000 molecular weight.

Olefin copolymers, are commercially available from Chevron OroniteCompany LLC under the trade designation “PARATONE®” (such as “PARATONE®8921” and “PARATONE® 8941”); from Afton Chemical Corporation under thetrade designation “HiTEC®” (such as “HiTEC® 5850B”; and from TheLubrizol Corporation under the trade designation “Lubrizol® 7067C”.Polyisoprene polymers are commercially available from InfineumInternational Limited, e.g. under the trade designation “SV200”;diene-styrene copolymers are commercially available from InfineumInternational Limited, e.g. under the trade designation “SV 260”.

In an embodiment of this disclosure, the viscosity index improvers maybe used in an amount of less than 2.0 weight percent, preferably lessthan 1.0 weight percent, and more preferably less than 0.5 weightpercent, based on the total weight of the formulated oil or lubricatingengine oil. Viscosity improvers are typically added as concentrates, inlarge amounts of diluent oil.

In another embodiment of this disclosure, the viscosity index improversmay be used in an amount of from 0.25 to 2.0 weight percent, preferably0.15 to 1.0 weight percent, and more preferably 0.05 to 0.5 weightpercent, based on the total weight of the formulated oil or lubricatingengine oil.

Detergents

Illustrative detergents useful in this disclosure include, for example,alkali metal detergents, alkaline earth metal detergents, or mixtures ofone or more alkali metal detergents and one or more alkaline earth metaldetergents. A typical detergent is an anionic material that contains along chain hydrophobic portion of the molecule and a smaller anionic oroleophobic hydrophilic portion of the molecule. The anionic portion ofthe detergent is typically derived from an organic acid such as a sulfuracid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof.The counterion is typically an alkaline earth or alkali metal.

Salts that contain a substantially stochiometric amount of the metal aredescribed as neutral salts and have a total base number (TBN, asmeasured by ASTM D2896) of from 0 to 80. Many compositions areoverbased, containing large amounts of a metal base that is achieved byreacting an excess of a metal compound (a metal hydroxide or oxide, forexample) with an acidic gas (such as carbon dioxide). Useful detergentscan be neutral, mildly overbased, or highly overbased. These detergentscan be used in mixtures of neutral, overbased, highly overbased calciumsalicylate, sulfonates, phenates and/or magnesium salicylate,sulfonates, phenates. The TBN ranges can vary from low, medium to highTBN products, including as low as 0 to as high as 600. Mixtures of low,medium, high TBN can be used, along with mixtures of calcium andmagnesium metal based detergents, and including sulfonates, phenates,salicylates, and carboxylates. A detergent mixture with a metal ratio of1, in conjunction of a detergent with a metal ratio of 2, and as high asa detergent with a metal ratio of 5, can be used. Borated detergents canalso be used.

Alkaline earth phenates are another useful class of detergent. Thesedetergents can be made by reacting alkaline earth metal hydroxide oroxide (CaO, Ca(OH)₂, BaO, Ba(OH)₂, MgO, Mg(OH)₂, for example) with analkyl phenol or sulfurized alkylphenol. Useful alkyl groups includestraight chain or branched C₁-C₃₀ alkyl groups, preferably, C₄-C₂₀ ormixtures thereof. Examples of suitable phenols include isobutylphenol,2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like. It shouldbe noted that starting alkylphenols may contain more than one alkylsubstituent that are each independently straight chain or branched andcan be used from 0.5 to 6 weight percent. When a non-sulfurizedalkylphenol is used, the sulfurized product may be obtained by methodswell known in the art. These methods include heating a mixture ofalkylphenol and sulfurizing agent (including elemental sulfur, sulfurhalides such as sulfur dichloride, and the like) and then reacting thesulfurized phenol with an alkaline earth metal base.

Metal salts of carboxylic acids are also useful as detergents. Thesecarboxylic acid detergents may be prepared by reacting a basic metalcompound with at least one carboxylic acid and removing free water fromthe reaction product. These compounds may be overbased to produce thedesired TBN level. Detergents made from salicylic acid are one preferredclass of detergents derived from carboxylic acids. Useful salicylatesinclude long chain alkyl salicylates. One useful family of compositionsis of the formula

where R is an alkyl group having 1 to 30 carbon atoms, n is an integerfrom 1 to 4, and M is an alkaline earth metal. Preferred R groups arealkyl chains of at least C₁₁, preferably C₁₃ or greater.

R may be optionally substituted with substituents that do not interferewith the detergent's function. M is preferably, calcium, magnesium, orbarium. More preferably, M is calcium.

Hydrocarbyl-substituted salicylic acids may be prepared from phenols bythe Kolbe reaction (see U.S. Pat. No. 3,595,791). The metal salts of thehydrocarbyl-substituted salicylic acids may be prepared by doubledecomposition of a metal salt in a polar solvent such as water oralcohol.

Alkaline earth metal phosphates are also used as detergents and areknown in the art.

Detergents may be simple detergents or what is known as hybrid orcomplex detergents. The latter detergents can provide the properties oftwo detergents without the need to blend separate materials. See U.S.Pat. No. 6,034,039.

Preferred detergents include calcium phenates, calcium sulfonates,calcium salicylates, magnesium phenates, magnesium sulfonates, magnesiumsalicylates and other related components (including borated detergents),and mixtures thereof. Preferred mixtures of detergents include magnesiumsulfonate and calcium salicylate, magnesium sulfonate and calciumsulfonate, magnesium sulfonate and calcium phenate, calcium phenate andcalcium salicylate, calcium phenate and calcium sulfonate, calciumphenate and magnesium salicylate, calcium phenate and magnesium phenate.

The detergent concentration in the lubricating oils of this disclosurecan range from 1.0 to 6.0 weight percent, preferably 2.0 to 5.0 weightpercent, and more preferably from 2.0 weight percent to 4.0 weightpercent, based on the total weight of the lubricating oil.

One particularly preferred detergent mixture for the inventivelubricating engine oil and the inventive method for improving fuelefficiency, frictional properties and deposit control is a combinationof an overbased calcium salicylate detergent and a magnesium sulfonateor a calcium sulfonate detergent. The overbased calcium salicylatedetergent may be included in the formulated oil at from 0.5 to 2.5 wt %,or 1.0 to 2.0 wt %, or 1.2 to 1.8 wt %. The magnesium sulfonate or acalcium sulfonate detergent may also be included in the formulated oilat from 0.5 to 2.5 wt %, or 1.0 to 2.0 wt %, or 1.2 to 1.8 wt %.

As used herein, the detergent concentrations are given on an “asdelivered” basis. Typically, the active detergent is delivered with aprocess oil. The “as delivered” detergent typically contains from 20weight percent to 80 weight percent, or from 40 weight percent to 60weight percent, of active detergent in the “as delivered” detergentproduct.

Dispersants

During engine operation, oil-insoluble oxidation byproducts areproduced. Dispersants help keep these byproducts in solution, thusdiminishing their deposition on metal surfaces. Dispersants used in theformulation of the lubricating oil may be ashless or ash-forming innature. Preferably, the dispersant is ashless. So-called ashlessdispersants are organic materials that form substantially no ash uponcombustion. For example, non-metal-containing or borated metal-freedispersants are considered ashless. In contrast, metal-containingdetergents discussed above form ash upon combustion.

Suitable dispersants typically contain a polar group attached to arelatively high molecular weight hydrocarbon chain. The polar grouptypically contains at least one element of nitrogen, oxygen, orphosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

A particularly useful class of dispersants are the alkenylsuccinicderivatives, typically produced by the reaction of a long chainhydrocarbyl substituted succinic compound, usually a hydrocarbylsubstituted succinic anhydride, with a polyhydroxy or polyaminocompound. The long chain hydrocarbyl group constituting the oleophilicportion of the molecule which confers solubility in the oil, is normallya polyisobutylene group. Many examples of this type of dispersant arewell known commercially and in the literature. Exemplary U.S. patentsdescribing such dispersants are U.S. Pat. Nos. 3,172,892; 3,215,707;3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012;3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersantare described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025;3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574;3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250;3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. Afurther description of dispersants may be found, for example, inEuropean Patent Application No. 471 071, to which reference is made forthis purpose.

Hydrocarbyl-substituted succinic acid and hydrocarbyl-substitutedsuccinic anhydride derivatives are useful dispersants. In particular,succinimide, succinate esters, or succinate ester amides prepared by thereaction of a hydrocarbon-substituted succinic acid compound preferablyhaving at least 50 carbon atoms in the hydrocarbon substituent, with atleast one equivalent of an alkylene amine are particularly useful,although on occasion, having a hydrocarbon substituent between 20-50carbon atoms can be useful.

Succinimides are formed by the condensation reaction between hydrocarbylsubstituted succinic anhydrides and amines. Molar ratios can varydepending on the polyamine. For example, the molar ratio of hydrocarbylsubstituted succinic anhydride to TEPA can vary from 1:1 to 5:1.Representative examples are shown in U.S. Pat. Nos. 3,087,936;3,172,892; 3,219,666; 3,272,746; 3,322,670; and U.S. Pat. Nos.3,652,616, 3,948,800; and Canada Patent No. 1,094,044.

Succinate esters are formed by the condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alcohols or polyols.Molar ratios can vary depending on the alcohol or polyol used. Forexample, the condensation product of a hydrocarbyl substituted succinicanhydride and pentaerythritol is a useful dispersant.

Succinate ester amides are formed by condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alkanol amines. Forexample, suitable alkanol amines include ethoxylatedpolyalkylpolyamines, propoxylated polyalkylpolyamines andpolyalkenylpolyamines such as polyethylene polyamines. One example ispropoxylated hexamethylenediamine. Representative examples are shown inU.S. Pat. No. 4,426,305.

The molecular weight of the hydrocarbyl substituted succinic anhydridesused in the preceding paragraphs will typically range between 800 and2,500 or more. The above products can be post-reacted with variousreagents such as sulfur, oxygen, formaldehyde, carboxylic acids such asoleic acid. The above products can also be post reacted with boroncompounds such as boric acid, borate esters or highly borateddispersants, to form borated dispersants generally having from 0.1 to 5moles of boron per mole of dispersant reaction product.

Mannich base dispersants are made from the reaction of alkylphenols,formaldehyde, and amines. See U.S. Pat. No. 4,767,551, which isincorporated herein by reference. Process aids and catalysts, such asoleic acid and sulfonic acids, can also be part of the reaction mixture.Molecular weights of the alkylphenols range from 800 to 2,500.Representative examples are shown in U.S. Pat. Nos. 3,697,574;3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.

Typical high molecular weight aliphatic acid modified Mannichcondensation products useful in this disclosure can be prepared fromhigh molecular weight alkyl-substituted hydroxyaromatics or HNR₂group-containing reactants.

Hydrocarbyl substituted amine ashless dispersant additives are wellknown to one skilled in the art; see, for example, U.S. Pat. Nos.3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.

Preferred dispersants include borated and non-borated succinimides,including those derivatives from mono-succinimides, bis-succinimides,and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbylsuccinimide is derived from a hydrocarbylene group such aspolyisobutylene having a Mn of from 500 to 5000, or from 1000 to 3000,or 1000 to 2000, or a mixture of such hydrocarbylene groups, often withhigh terminal vinylic groups. Other preferred dispersants includesuccinic acid-esters and amides, alkylphenol-polyamine-coupled Mannichadducts, their capped derivatives, and other related components. Suchadditives may be used in an amount of 0.1 to 20 weight percent,preferably 0.5 to 8 weight percent, or more preferably 0.5 to 4 weightpercent. On an active ingredient basis, such additives may be used in anamount of 0.06 to 14 weight percent, preferably 0.3 to 6 weight percent.The hydrocarbon portion of the dispersant atoms can range from C₆₀ toC₄₀₀, or from C₇₀ to C₃₀₀, or from C₇₀ to C₂₀₀. These dispersants maycontain both neutral and basic nitrogen, and mixtures of both.Dispersants can be end-capped by borates and/or cyclic carbonates.

One particularly preferred dispersant for the inventive lubricatingengine oil and the inventive method for improving fuel efficiency,frictional properties and deposit control is a non-boratedpolyisobutenyl bis-succinimide (PIBSA) dispersant. The non-borated PIBSAdispersant may be included in the formulated oil at from 2.0 to 6.0 wt%, or 3.0 to 5.0 wt %, or 3.5 to 4.5 wt %.

As used herein, the dispersant concentrations are given on an “asdelivered” basis. Typically, the active dispersant is delivered with aprocess oil. The “as delivered” dispersant typically contains from 20weight percent to 80 weight percent, or from 40 weight percent to 60weight percent, of active dispersant in the “as delivered” dispersantproduct.

Further Antioxidants

Antioxidants retard the oxidative degradation of base oils and additivesduring service. Such degradation may result in deposits on metalsurfaces, the presence of sludge, or a viscosity increase in thelubricant. One skilled in the art knows a wide variety of oxidationinhibitors that are useful in lubricating oil compositions. See, Klamannin Lubricants and Related Products, op cite, and U.S. Pat. Nos.4,798,684 and 5,084,197, for example.

Useful antioxidants may include hindered phenols. These phenolicantioxidants may be ashless (metal-free) phenolic compounds or neutralor basic metal salts of certain phenolic compounds. Typical phenolicantioxidant compounds are the hindered phenolics which are the oneswhich contain a sterically hindered hydroxyl group, and these includethose derivatives of dihydroxy aryl compounds in which the hydroxylgroups are in the o- or p-position to each other. Typical phenolicantioxidants may include the hindered phenols substituted with C₆+alkylgroups and the alkylene coupled derivatives of these hindered phenols.Examples of phenolic materials of this type 2-t-butyl-4-heptyl phenol;2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol;2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecylphenol. Other useful hindered mono-phenolic antioxidants may include forexample hindered 2,6-di-alkyl-phenolic propionic ester derivatives.Bis-phenolic antioxidants may also be advantageously used in combinationwith the instant disclosure. Examples of ortho-coupled phenols include:2,2′-bis(4-heptyl-6-t-butyl-phenol); 2,2′-bis(4-octyl-6-t-butyl-phenol);and 2,2′-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenolsinclude for example 4,4′-bis(2,6-di-t-butyl phenol) and4,4′-methylene-bis(2,6-di-t-butyl phenol).

Effective amounts of one or more catalytic antioxidants may also beused. The catalytic antioxidants comprise an effective amount of a) oneor more oil soluble polymetal organic compounds; and, effective amountsof b) one or more substituted N,N′-diaryl-o- phenylenediamine compoundsor c) one or more hindered phenol compounds; or a combination of both b)and c). Catalytic antioxidants are more fully described in U.S. Pat. No.8,048,833, herein incorporated by reference in its entirety.

Non-phenolic oxidation inhibitors which may be used include aromaticamine antioxidants and these may be used either as such or incombination with phenolics. Typical examples of non-phenolicantioxidants may include: alkylated and non-alkylated aromatic aminessuch as aromatic monoamines of the formula R⁸R⁹R¹⁰N where R⁸ is analiphatic, aromatic or substituted aromatic group, R⁹ is an aromatic ora substituted aromatic group, and R¹° is H, alkyl, aryl orR11S(O)_(X)R¹² where R¹¹ is an alkylene, alkenylene, or aralkylenegroup, R¹² is a higher alkyl group, or an alkenyl, aryl, or alkarylgroup, and x is 0, 1 or 2. The aliphatic group R⁸ may contain from 1 to20 carbon atoms, and preferably contains from 6 to 12 carbon atoms. Thealiphatic group is a saturated aliphatic group. Preferably, both R⁸ andR⁹ are aromatic or substituted aromatic groups, and the aromatic groupmay be a fused ring aromatic group such as naphthyl. Aromatic groups R⁸and R⁹ may be joined together with other groups such as S.

Typical aromatic amines antioxidants have alkyl substituent groups of atleast 6 carbon atoms. Examples of aliphatic groups include hexyl,heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups willnot contain more than 14 carbon atoms. The general types of amineantioxidants useful in the present compositions include diphenylamines,phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenylphenylene diamines. Mixtures of two or more aromatic amines are alsouseful. Polymeric amine antioxidants can also be used. Particularexamples of aromatic amine antioxidants useful in the present disclosureinclude: p,p′-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine;phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.

Sulfurized alkyl phenols and alkali or alkaline earth metal saltsthereof also are useful antioxidants.

Preferred antioxidants may include hindered phenols, arylamines. Theseantioxidants may be used individually by type or in combination with oneanother. Such additives may be used in an amount of 0.01 to 5 weightpercent, preferably 0.01 to 1.5 weight percent, more preferably zero toless than 1.5 weight percent, more preferably zero to less than 1 weightpercent.

Pour Point Depressants (PPDs)

Conventional pour point depressants (also known as lube oil flowimprovers) may be added to the compositions of the present disclosure ifdesired. These pour point depressant may be added to lubricatingcompositions of the present disclosure to lower the minimum temperatureat which the fluid will flow or can be poured. Examples of suitable pourpoint depressants include polymethacrylates, polyacrylates,polyarylamides, condensation products of haloparaffin waxes and aromaticcompounds, vinyl carboxylate polymers, and terpolymers ofdialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479;2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pourpoint depressants and/or the preparation thereof. Such additives may beused in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5weight percent.

Seal Compatibility Agents

Seal compatibility agents help to swell elastomeric seals by causing achemical reaction in the fluid or physical change in the elastomer.Suitable seal compatibility agents for lubricating oils include organicphosphates, alkoxysulfonlanes (C₁₀ alcohol, for example), aromaticesters, aromatic hydrocarbons, esters (butylbenzyl phthalate, forexample), and polybutenyl succinic anhydride. Such additives may be usedin an amount of 0.01 to 3 weight percent, preferably 0.01 to 2 weightpercent.

Antifoam Agents

Antifoam agents may advantageously be added to lubricant compositions.These agents retard the formation of stable foams. Silicones and organicpolymers are typical antifoam agents. For example, polysiloxanes, suchas silicon oil or polydimethyl siloxane, provide antifoam properties.Antifoam agents are commercially available and may be used inconventional minor amounts along with other additives such asdemulsifiers; usually the amount of these additives combined is lessthan 1 weight percent and often less than 0.1 weight percent.

Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protectlubricated metal surfaces against chemical attack by water or othercontaminants. A wide variety of these are commercially available.

One type of antirust additive is a polar compound that wets the metalsurface preferentially, protecting it with a film of oil. Another typeof antirust additive absorbs water by incorporating it in a water-in-oilemulsion so that only the oil touches the metal surface. Yet anothertype of antirust additive chemically adheres to the metal to produce anon-reactive surface. Examples of suitable additives include zincdithiophosphates, metal phenolates, basic metal sulfonates, fatty acidsand amines. Such additives may be used in an amount of 0.01 to 5 weightpercent, preferably 0.01 to 1.5 weight percent.

Friction Modifiers

A friction modifier is any material or materials that can alter thecoefficient of friction of a surface lubricated by any lubricant orfluid containing such material(s). Friction modifiers, also known asfriction reducers, or lubricity agents or oiliness agents, and othersuch agents that change the ability of base oils, formulated lubricantcompositions, or functional fluids, to modify the coefficient offriction of a lubricated surface may be effectively used in combinationwith the base oils or lubricant compositions of the present disclosureif desired. Friction modifiers that lower the coefficient of frictionare particularly advantageous in combination with the base oils and lubecompositions of this disclosure.

Illustrative friction modifiers may include, for example, organometalliccompounds or materials, or mixtures thereof. Illustrative organometallicfriction modifiers useful in the lubricating engine oil formulations ofthis disclosure include, for example, molybdenum amine, molybdenumdiamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenumdithiophosphates, molybdenum amine complexes, molybdenum carboxylates,and the like, and mixtures thereof. Similar tungsten based compounds maybe preferable. [00152] Other illustrative friction modifiers useful inthe lubricating engine oil formulations of this disclosure include, forexample, alkoxylated fatty acid esters, alkanolamides, polyol fatty acidesters, borated glycerol fatty acid esters, fatty alcohol ethers, andmixtures thereof.

Illustrative alkoxylated fatty acid esters include, for example,polyoxyethylene stearate, fatty acid polyglycol ester, and the like.These can include polyoxypropylene stearate, polyoxybutylene stearate,polyoxyethylene isosterate, polyoxypropylene isostearate,polyoxyethylene palmitate, and the like.

Illustrative alkanolamides include, for example, lauric aciddiethylalkanolamide, palmic acid diethylalkanolamide, and the like.These can include oleic acid diethyalkanolamide, stearic aciddiethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylatedhydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.

Illustrative polyol fatty acid esters include, for example, glycerolmono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerolmono-stearate, and the like. These can include polyol esters,hydroxyl-containing polyol esters, and the like.

Illustrative borated glycerol fatty acid esters include, for example,borated glycerol mono-oleate, borated saturated mono-, di-, andtri-glyceride esters, borated glycerol mono-stearate, and the like. Inaddition to glycerol polyols, these can include trimethylolpropane,pentaerythritol, sorbitan, and the like. These esters can be polyolmonocarboxylate esters, polyol dicarboxylate esters, and on occasionpolyoltricarboxylate esters. Preferred can be the glycerol mono-oleates,glycerol dioleates, glycerol trioleates, glycerol monostearates,glycerol distearates, and glycerol tristearates and the correspondingglycerol monopalmitates, glycerol dipalmitates, and glyceroltripalmitates, and the respective isostearates, linoleates, and thelike. On occasion the glycerol esters can be preferred as well asmixtures containing any of these. Ethoxylated, propoxylated, butoxylatedfatty acid esters of polyols, especially using glycerol as underlyingpolyol can be preferred.

Illustrative fatty alcohol ethers include, for example, stearyl ether,myristyl ether, and the like. Alcohols, including those that have carbonnumbers from C₃ to C₅₀, can be ethoxylated, propoxylated, or butoxylatedto form the corresponding fatty alkyl ethers. The underlying alcoholportion can preferably be stearyl, myristyl, C₁₁-C₁₃ hydrocarbon, oleyl,isosteryl, and the like.

Useful concentrations of friction modifiers may range from 0.01 weightpercent to 5 weight percent, or about 0.1 weight percent to about 2.5weight percent, or about 0.1 weight percent to about 1.5 weight percent,or about 0.1 weight percent to about 1 weight percent.

Concentrations of molybdenum-containing materials are often described interms of Mo metal concentration. Advantageous concentrations of Mo mayrange from 25 ppm to 700 ppm or more, and often with a preferred rangeof 50-200 ppm. Friction modifiers of all types may be used alone or inmixtures with the materials of this disclosure. Often mixtures of two ormore friction modifiers, or mixtures of friction modifier(s) withalternate surface active material(s), are also desirable.

When lubricating oil compositions contain one or more of the additivesdiscussed above, the additive(s) are blended into the composition in anamount sufficient for it to perform its intended function. Typicalamounts of such additives useful in the present disclosure are shown inthe table below.

It is noted that many of the additives are shipped from the additivemanufacturer as a concentrate, containing one or more additivestogether, with a certain amount of base oil diluents. Accordingly, theweight amounts in the table below, as well as other amounts mentionedherein, are directed to the amount of active ingredient (that is thenon-diluent portion of the ingredient). The weight percent (wt %)indicated below is based on the total weight of the lubricating oilcomposition.

compound useful amount typical amount dispersant  0.1-20 0.1-8 detergent  0.1-20 0.1-8  friction modifier 0.01-5  0.01-1.5 antioxidant0.1-5  0.1-1.5 pour point depressant  0-5 0.01-1.5 anti-foam agent0.001-3  0.001-0.15 viscosity index improver 0.1-2 0.1-1  anti-wear0.1-2 0.5-1  inhibitor and antirust 0.01-5  0.01-1.5

The foregoing additives are all commercially available materials. Theseadditives may be added independently but are usually precombined inpackages which can be obtained from suppliers of lubricant oiladditives. Additive packages with a variety of ingredients, proportionsand characteristics are available and selection of the appropriatepackage will take the requisite use of the ultimate composition intoaccount.

The present antioxidant compositions can be introduced into thelubricating oil in manners known per se. The compounds are readilysoluble in oils. They may be added directly to the lubricating oil orthey can be diluted with a substantially inert, normally liquid organicdiluent such as naphtha, benzene, toluene, xylene or a normally liquidoil or fuel to form an additive concentrate or masterbatch. Antioxidantconcentrates may include base stocks, such as ester base stocks, as adiluent. In certain embodiments, antioxidant concentrates includesolvents such as glymes, such as monomethyl tetraglyme. Theseconcentrates generally contain from about 10% to about 90% by weightadditive and may contain one or more other additional additives. Thepresent antioxidant compositions may be introduced as part of anadditive package in liquid or solid form.

The antioxidant polymer (e.g., oligomer) compositions of this disclosuremay advantageously be diluted with one or more liquid additivesdisclosed herein, for instance one or more liquid dispersants,detergents, antiwear additives, corrosion inhibitors or antioxidantsmentioned herein to prepare an antioxidant additive package. Liquidantioxidants may include certain aminic and phenolic antioxidants.Further aminic and phenolic antioxidants may include one or more ofN,N-di-(p-tert-butylphenyl)amine, N,N-di-(p-tert-octylphenyl)amine,N-(p-tert-butylphenyl)-N-phenylamine,N-(p-tert-octylphenyl)-N-phenylamine andN-(p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine,bis-nonylphenyldiphenylamine, N-(tert-C₁-C₂₀alkylphenyl)-1-naphthylamineand 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid octyl ester.

In some embodiments, the amount of polymer (e.g., oligomer) to be addedto a base oil is that to provide a desired good balance of depositsperformance, good color and viscosity control. For instance, aneffective amount of polymer (e.g., oligomer) is from about 0.01 wt %,about 0.05, about 0.1, about 0.3, about 0.5, about 0.7, about 1.0, about1.5, about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5,about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about8.0, about 8.5 or about 9.0 wt % to about 10, about 11, about 12, about13, about 14, about 15, about 16, about 17, about 18, about 19 or about20 wt % of the polymer (e.g., oligomer), based on the total weight ofthe lubricating oil composition.

The lubricating oil compositions are in some embodiments engine oilshaving a kinematic viscosity at 100° C. of from any one of about 2 cSt,about 3 cSt, about 4 cSt, about 5 cSt, about 6 cSt or about 7 cSt to anyone of about 8 cSt, about 9 cSt, about 10 cSt, about 11 cSt, about 12cSt, about 13 cSt, about 14 cSt, about 15 cSt, about 16 cSt, about 17cSt, about 18 cSt, about 19 cSt or about 20 cSt.

Greases

The compositions of the present disclosure may include a thickener(e.g., a water-insoluble thickener) in a range from about 0.5 to about20 wt. % (e.g., about 0.5 to about 10 wt. %. For example, the greasecomposition of the present disclosure may have thickener present in anamount of about 0.5 wt. % to about 20 wt. %, about 0.5 wt. % to about17.5 wt. %, about 0.5 wt. % to about 15 wt. %, about 0.5 wt. % to about12.5 wt. %, about 0.5 wt. % to about 10 wt. %, about 0.5 wt. % to about7.5 wt. %, about 0.5 wt. % to about 5 wt. %, about 1 wt. % to about 20wt. %, about 1 wt. % to about 17.5 wt. %, about 1 wt. % to about 15 wt.%, about 1 wt. % to about 12.5 wt. %, about 1 wt. % to about 10 wt. %,about 1 wt. % to about 7.5 wt. %, about 1 wt. % to about 5 wt. %, about2.5 wt. % to about 20 wt. %, about 2.5 wt. % to about 17.5 wt. %, about2.5 wt. % to about 15 wt. %, about 2.5 wt. % to about 12.5 wt. %, about2.5 wt. % to about 10 wt. %, about 2.5 wt. % to about 7.5 wt. %, about 5wt. % to about 20 wt. %, about 5 wt. % to about 17.5 wt. %, about 5 wt.% to about 15 wt. %, about 5 wt. % to about 12.5 wt. %, about 5 wt. % toabout 10 wt. %, about 7.5 wt. % to about 20 wt. %, about 7.5 wt. % toabout 17.5 wt. %, about 7.5 wt. % to about 15 wt. %, about 7.5 wt. % toabout 12.5 wt. %, about 10 wt. % to about 20 wt. %, about 10 wt. % toabout 17.5 wt. %, about 10 wt. % to about 15 wt. %, about 12.5 wt. % toabout 20 wt. %, about 12.5 wt. % to about 17.5 wt. %, or about 15 wt. %to about 20 wt. %.

The grease will contain an essentially water- and oil-insolublethickener to provide the desired grease consistency and structure (conepenetration, dropping point, etc.). Thickeners may be of the soap ornon-soap types. Non-soaps are based on organic or non-organic solidssuch as bentonite clay, polymers such as the polyureas or silicaaerogels and may be used where their particular properties so indicate.For example, thickeners for the present greases are the metal salt/soapthickeners, including the complex soap thickeners based on metalsincluding aluminum, barium, calcium, lithium, sodium. These types ofthickeners are well established and are described in numerouspublications. See, for example, Boner op cit, Lubricants and RelatedProducts, Klamann, Verlag Chemie, 1984, ISBN 3-527-26022-6, ISBN0-89573-177-0 to which reference is made for a description of suitablethickeners and the manufacture of grease incorporating them.

Complex grease thickeners are made by combining the conventionalmetallic soaps with a complexing agent. The soaps may be a metal salt ofa long chain fatty acid having from 8 to 24 carbon atoms such asdecanoic acid, myristic acid, palmitic acid or stearic acid. Thethickener may be a lithium or lithium complex thickener thatincorporates a hydroxy fatty acid having from 12 to 24 (e.g., from 16 to20) carbon atoms. For example, the hydroxy fatty acid may be an hydroxystearic acid, e.g., 9-hydroxy or 10-hydroxy stearic acid, or 12-hydroxystearic acid. Other hydroxyl fatty acids which may be used includericinoleic acid (12-hydoxystearic acid unsaturated at the 9,10position), 12-hydroxybehenic acid and 10-hydroxypalmitic acid. Thecomplex salt/soap thickeners are made with a combination of conventionallithium soap such as lithium 12-hydroxystearate and a complexing agentwhich may vary with the type of thickener, e.g. calcium complexthickeners may be formulated with acetic acid and hydroxy-substitutedacids; boric acid may be used with lithium soaps. Low molecular-weightorganic acid, typically C₄ to C₁₂ dibasic acids such as glutaric,azelaic, pimelic, suberic, adipic or sebacic acids, are generallyfavored as the complexing agents with lithium greases. The complexes areformed by the introduction of the complexing agent or its metal saltinto the lattice of the metal salt. Examples of metal salt/soap complexthickeners are described in U.S. Pat. No. 3,929,651; 3,940,339;4,410,435; 4,444,669 and 5,731,274. The complexing agent may be added asthe free acid, a salt e.g., the lithium salt or as an ester such as analkyl ester, e.g. methyl glutarate or methyl adipate, which will undergohydrolysis to the acid in the presence of the added alkali, e.g. lithiumhydroxide, to form the complexing agent. PAO bases may require a higherproportion of thickener than mineral oil base stocks.

The lithium complex thickener used in the grease of the presentdisclosure is not particularly limited and can be any lithium complexthickener that is known or that becomes known. For example, the lithiumcomplex thickener can comprise a lithium soap derived from a fatty acidhaving: (a) (i) at least one of an epoxy group, ethylenic unsaturation,or a combination thereof, and (ii) a dilithium salt derived from astraight chain dicarboxylic acid; and/or (b) a lithium salt derived froma hydroxy-substituted carboxylic acid, e.g. salicylic acid.

For example, the lithium complex thickener can comprise at least one of:a complex of a lithium soap of a C₁₂ to C₂₄ hydroxy fatty acid and amonolithium salt of boric acid; a lithium salt of a second hydroxycarboxylic acid, such as salicylic acid; or a combination thereof.

The lithium complex thickener can comprise a lithium soap of a C₁₂ toC₂₄ hydroxy fatty acid thickener antioxidant having an alkali metal saltof hydroxy benzoic acid and a diozime compound. In certain embodiments,the alkali metal salt of hydroxy benzoic acid includes dilithiumsalicylate.

The lithium complex thickener can be a lithium soap comprising at leastone of: a dilithium salt of a C₄ to C₁₂ dicarboxylic acid, e.g.,dilithium azelate; a lithium soap of a 9-, 10- or 12-hydroxy C₁₂ to C₂₄fatty acid, e.g., lithium 12-hydroxy stearate; and a lithium salt formedin-situ in the grease from a second hydroxy carboxylic acid, wherein the—OH group is attached to a carbon atom not more than 6 carbons removedfrom the carboxyl group and either of those groups can be attached toaliphatic portions of the materials or aromatic portions of thematerials.

In any aspect or embodiment described herein, the lithium complexthickener can comprise a complex lithium thickener and at least one of alithium salt of a C₃ to C₁₄ hydroxycarboxylic acid, a thiadiazole, or acombination thereof.

In any aspect or embodiment described herein, the water insolublethickener may include at least one of an aluminum soap, a barium soap, acalcium soap, a lithium soap, an aluminum salt/soap complex, a bariumsalt/soap complex, a calcium salt/soap complex, a lithium salt/soapcomplex, or a combination thereof.

The grease composition of the present disclosure comprises a lowmolecular weight thixotropic polyamide composition as a co-thickener,which contributes to the formation of the thickener matrix. Thethixotrope is essentially insoluble in water and oil in order tomaintain the grease structure and the desired resistance to water washout. Thixotropes create a viscosity increase that is reversed duringshearing, but then reforms when the shear forces are removed. Thischaracteristic has been found to provide advantageous properties whenused in combination with the remaining grease components.

In any aspect or embodiment described herein, the composition of thepresent disclosure comprises less than or equal to about 1.25 wt. % ofthe low molecular weight thixotropic polyamide composition. For example,the low molecular weight thixotropic polyamide composition may bepresent in an amount of less than or equal to about 1.10 wt. %, lessthan or equal to about 1 wt. %, less than or equal to about 0.75 wt. %,less than or equal to about 0.50 wt. %, or less than or equal to about0.25 wt. %.

In any aspect or embodiment described herein, the thixotropic polyamidecomposition of the present disclosure may have a (O—H+N—H) to C—H peakintensity ratio of ≥ about 0.5. For example, the (O—H+N—H) to C—H peakintensity ratio of the low molecular weight thixotropic polyamide may be≥ about 0.55, ≥ about 0.6, ≥ about 0.65, ≥ about 0.7, or ≥ about 0.75.In any aspect or embodiment described herein, the thixotropic polyamidecomposition of the present disclosure may have at least one of:

≤ about 8 wt. % (e.g., about 5 wt. % or ≤ about 4 wt. %) of amidematerial having a molecular weight of at least about 1700;

≤ about 25 wt. % (e.g., ≤ about 20 wt. % or ≤ about 17.5 wt. %) of amidematerial having a molecular weight of about 1100 to about 1300;

≥ about 70 wt. % (e.g., ≥ about 75 wt. % or ≥ about 80 wt. %) of amidematerial having a molecular weight of about 1000 or less (e.g., about 50wt. % to about 80 wt. % of the amide material having a molecular weightof about 700 to about 1000); or a combination thereof.

In any aspect or embodiment described here, the low molecular weightthixotropic polyamide composition has amide material with a molecularweight of about 700 to about 1000 present in an amount of about 50 wt. %to about 80 wt. %, about 50 wt. % to about 70 wt. %, about 50 wt. % toabout 60 wt. %, about 60 wt. % to about 80 wt. %, about 60 wt. % toabout 70 wt. %, or about 70 wt. % to about 80 wt. %.

The composition of the present disclosure may include small amounts ofat least one (e.g., 1, 2, 3, 4, 5, or 6, or more) performance additive.For example, the composition of the present disclosure may include atleast one of anticorrosive agent or corrosion inhibitor, an extremepressure additive, an antiwear agent, a pour point depressants, anantioxidant or oxidation inhibitor, a rust inhibitor, a metaldeactivator, a dispersant, a demulsifier, a dye or colorant/chromophoricagent, a seal compatibility agent, a friction modifier, a viscositymodifier/improver, a viscosity index improver, or combinations thereof.For example, solid lubricants such as molybdenum disulfide and graphitemay be present in the composition of the present disclosure, such asfrom about 1 to about 5 wt. % (e.g., from about 1.5 to about 3 wt. %)for molybdenum disulfide and from about 3 to about 15.wt. % (e.g., fromabout 6 to about 12 wt. %) for graphite.

The amounts of individual additives will vary according to the additiveand the level of functionality to be provided by it.

The presence or absence of these lubricating oil performance additivesdoes not adversely affect the compositions of the present disclosure.For a review of many commonly used additives, see Klamann in Lubricantsand Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN 0 89573177 0. Reference is also made to “Lubricant Additives” by M. W. Ranney,published by Noyes Data Corporation of Parkridge, N.J. (1973) and“Lubricant Additives: Chemistry and Applications” edited by L. R.Rudnick, published by CRC Press of Boca Raton, Fla. (2009). Theperformance additives useful in the present disclosure do not have to besoluble in the lubricating oils. Insoluble additives in oil can bedispersed in the lubricating oils of the present disclosure. The typesand quantities of performance additives used in combination with thecompositions of the present disclosure are not limited by the examplesshown herein as illustrations.

As such, in any aspect or embodiment described herein, the compositionfurther comprises at least one of anticorrosive agent or corrosioninhibitor, an extreme pressure additive, an antiwear agent, a pour pointdepressants, an antioxidant or oxidation inhibitor, a rust inhibitor, ametal deactivator, a dispersant, a demulsifier, a dye orcolorant/chromophoric agent, a seal compatibility agent, a frictionmodifier, a viscosity modifier/improver, a viscosity index improver, orcombinations thereof. In any aspect or embodiment described herein, thedispersant includes succinimide-type dispersant. Unless specifiedotherwise, the performance additive or performance additives listedabove are present in a total amount equal to or less than about 10 wt.%, equal to or less than about 9.5 wt. %, equal to or less than about 9wt. %, equal to or less than about 8.5 wt. %, equal to or less thanabout 8 wt. %, equal to or less than about 7.5 wt. %, equal to or lessthan about 7 wt. %, equal to or less than about 6.5 wt. %, equal to orless than about 6 wt. %, equal to or less than about 5.5 wt. %, equal toor less than about 5 wt. %, equal to or less than about 4.5 wt. %, equalto or less than about 4 wt. %, equal to or less than about 3.5 wt. %,equal to or less than about 3 wt. %, equal to or less than about 2.5 wt.%, equal to or less than about 2 wt. %, equal to or less than about 1.5wt. %, or equal to or less than about 0.5 wt. %. For example, theperformance additive or performance additives are present in a totalamount of about 0.1 to about 10 wt. %, about 0.1 to about 9 wt. %, about0.1 to about 8 wt. %, about 0.1 to about 7 wt. %, about 0.1 to about 6wt. %, about 0.1 to about 5 wt. %, about 0.1 to about 4 wt. %, about 0.1to about 3 wt. %, about 0.1 to about 2 wt. %, about 0.1 to about 1 wt.%, about 0.5 to about 10 wt. %, about 0.5 to about 9 wt. %, about 0.5 toabout 8 wt. %, about 0.5 to about 7 wt. %, about 0.5 to about 6 wt. %,about 0.5 to about 5 wt. %, about 0.5 to about 4 wt. %, about 0.5 toabout 3 wt. %, about 0.5 to about 2 wt. %, about 1 to about 10 wt. %,about 1 to about 9 wt. %, about 1 to about 8 wt. %, about 1 to about 7wt. %, about 1 to about 6 wt. %, about 1 to about 5 wt. %, about 1 toabout 4 wt. %, about 1 to about 3 wt. %, about 2 to about 10 wt. %,about 2 to about 9 wt. %, about 2 to about 8 wt. %, about 2 to about 7wt. %, about 2 to about 6 wt. %, about 2 to about 5 wt. %, about 2 toabout 4 wt. %, about 3 to about 10 wt. %, about 3 to about 9 wt. %,about 3 to about 8 wt. %, about 3 to about 7 wt. %, about 3 to about 6wt. %, about 3 to about 5 wt. %, about 4 to about 10 wt. %, about 4 toabout 9 wt. %, about 4 to about 8 wt. %, about 4 to about 7 wt. %, about4 to about 6 wt. %, about 5 to about 10 wt. %, about 5 to about 9 wt. %,about 5 to about 8 wt. %, about 5 to about 7 wt. %, about 6 to about 10wt. %, about 6 to about 9 wt. %, about 6 to about 8 wt. %, about 7 toabout 10 wt. %, about 7 to about 9 wt. %, or about 8 to about 10 wt. %.

When the additives are described below by reference to individualcomponents used in the formulation, they will not necessarily be presentor identifiable as discrete entities in the final product but may bepresent as reaction products which are formed during the greasemanufacture or even its use. This will depend on the respectivechemistries of the ingredients, their stoichiometry, and thetemperatures encountered in the grease making process or during its use.It will also depend, naturally enough, on whether or not the species areadded as a pre-reacted additive package. For example, the acid aminephosphates may be added as discrete amines and acid phosphates but thesemay react to form a new entity in the final grease composition under theprocessing conditions used in the grease manufacture.

Viscosity Improver(s) or Modifier(s). In any aspect or embodimentdescribed herein, the composition of the present disclosure comprises atleast one viscosity improver or modifier (e.g., 1, 2, 3, 4, 5, 6, ormore viscosity improver or modifier). The viscosity improver, viscositymodifier, or Viscosity Index (VI) modifier increases the viscosity ofthe composition of the present disclosure at elevated temperatures,thereby increasing film thickness, and having limited effects on theviscosity of the composition of the present disclosure at lowtemperatures. In certain embodiments, the composition of the presentdisclosure comprises at least one viscosity improver (e.g., 1, 2, 3, 4,5, 6, or more viscosity improver(s)). Any viscosity improver that isknown or that becomes known in the art may be utilized in thecomposition of the present disclosure. Exemplary viscosity improversinclude high molecular weight hydrocarbons, polyesters and viscosityindex improver dispersants that function as both a viscosity indeximprover and a dispersant. The molecular weight of these polymers canrange from about 1,000 to about 1,500,000 (e.g., about 20,000 to about1,200,000 or about 50,000 to about 1,000,000). In a particularembodiment, the molecular weights of these polymers can range from about1,000 to about 1,000,000 (e.g., about 1,200 to about 500,000 or about1,200 to about 5,000).

In certain embodiments, the viscosity improver is at least one of linearor star-shaped polymers of methacrylate, linear or star-shapedcopolymers of methacrylate, butadiene, olefins, alkylated styrenes,polyisobutylene, polymethacrylate (e.g., copolymers of various chainlength alkyl methacrylates), copolymers of ethylene and propylene,hydrogenated block copolymers of styrene and isoprene, or combinationsthereof. For example, the viscosity improver may includestyrene-isoprene or styrene-butadiene based polymers of about 50,000 toabout 200,000 molecular weight.

Olefin copolymers are commercially available from Chevron OroniteCompany LLC under the trade designation “PARATONE®” (such as “PARATONE®8921” and “PARATONE® 8941”); from Afton Chemical Corporation under thetrade designation “HiTEC®” (such as “HiTEC® 5850B”); and from TheLubrizol Corporation under the trade designation “Lubrizol® 7067C”.Hydrogenated polyisoprene star polymers are commercially available fromInfineum International Limited, e.g., under the trade designation“SV200” and “SV600”. Hydrogenated diene-styrene block copolymers arecommercially available from Infineum International Limited, e.g., underthe trade designation “SV 50”.

The polymethacrylate or polyacrylate polymers can be linear polymerswhich are available from Evnoik Industries under the trade designation“Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which areavailable from Lubrizol Corporation under the trade designation Asteric™(e.g., Lubrizol 87708 and Lubrizol 87725).

Illustrative vinyl aromatic-containing polymers useful in the presentdisclosure may be derived predominantly from vinyl aromatic hydrocarbonmonomer. Illustrative vinyl aromatic-containing copolymers useful in thepresent disclosure may be represented by the following formula:

A-B,

wherein:

A is a polymeric block derived predominantly from vinyl aromatichydrocarbon monomer, and

B is a polymeric block derived predominantly from conjugated dienemonomer.

Although their presence is not required to obtain the benefit of thecomposition of the present disclosure, viscosity modifiers may be usedin an amount of less than about 10 weight percent (e.g. less than about7 weight percent or less than about 4 weight percent). In certainembodiments, the viscosity improver is present in an amount less than 2weight percent, less than about 1 weight percent, or less than about 0.5weight percent, based on the total weight of the composition of thepresent disclosure. Viscosity modifiers are generally added asconcentrates, in large amounts of diluent oil.

As used herein, the viscosity modifier concentrations are given on an“as delivered” basis. The active polymer may be delivered with a diluentoil. The “as delivered” viscosity modifier may contain from about 20weight percent to about 75 weight percent of an active polymer forpolymethacrylate or polyacrylate polymers, or from about 8 weightpercent to about 20 weight percent of an active polymer for olefincopolymers, hydrogenated polyisoprene star polymers, or hydrogenateddiene-styrene block copolymers, in the “as delivered” polymerconcentrate.

Demulsifier(s). In any aspect or embodiment described herein, thecomposition of the present disclosure comprises at least one (e.g., 1,2, 3, or 4, or more) demulsifier. The demulsifier may be added toseparate emulsions (e.g., water-in-oil). Any demulsifier that is knownor that becomes know may be utilized in the composition of the presentdisclosure. An illustrative demulsifying component is described inEP-A-330,522. This exemplary demulsifying agent is obtained by reactingan alkylene oxide with an adduct obtained by reaction of a bis-epoxidewith a polyhydric alcohol. Demulsifiers are commercially available andmay be used in conventional minor amounts along with other additivessuch as antifoam agents. Although their presence is not required toobtain the benefit of the present disclosure, the emulsifier oremulsifiers may be present a combined amount less than 1 weight percent(e.g. less than 0.1 weight percent).

In certain embodiments, the demulsifying agent includes at least one ofalkoxylated phenols, phenol-formaldehyde resins, synthetic alkylarylsulfonates (such as metallic dinonylnaphthalene sulfonates), or acombination thereof. In an embodiment, a demulsifing agent is apredominant amount of a water-soluble polyoxyalkylene glycol having apre-selected molecular weight of any value in the range of between about450 and about 5000 or more. In an embodiment, the water solublepolyoxyalkylene glycol demulsifier may also be one produced fromalkoxylation of n-butanol with a mixture of alkylene oxides to form arandom alkoxylated product.

Polyoxyalkylene glycols useful in the present disclosure may be producedby a well- known process for preparing polyalkylene oxide havinghydroxyl end-groups by subjecting an alcohol or a glycol ether and oneor more alkylene oxide monomers, such as ethylene oxide, butylene oxide,or propylene oxide, to form block copolymers in addition polymerization,while employing a strong base, such as potassium hydroxide as acatalyst. In such a process, the polymerization is commonly carried outunder a catalytic concentration of about 0.3 to about 1.0% by mole ofpotassium hydroxide to the monomer(s) and at high temperature of about100° C. to about 160° C. It is well known that the catalyst potassiumhydroxide is, for the most part, bonded to the chain-end of the producedpolyalkylene oxide in a form of alkoxide in the polymer solution soobtained.

The soluble polyoxyalkylene glycol emulsifier(s) useful in thecompositions of the present disclosure may also be one produced fromalkoxylation of n-butanol with a mixture of alkylene oxides to form arandom alkoxylated product.

Extreme Pressure Agent(s). In any aspect or embodiment described herein,the composition of the present disclosure comprises at least one (e.g.,1, 2, 3, or 4, or more) extreme pressure agent. Any extreme pressureagent that is known or that becomes know may be utilized in thecomposition of the present disclosure.

The extreme pressure agents can be at least one sulfur-based extremepressure agents, such as sulfides, sulfoxides, sulfones,thiophosphinates, thiocarbonates, sulfurized fats and oils, sulfurizedolefins, the like, or combinations thereof; at least onephosphorus-based extreme pressure agents, such as phosphoric acid esters(e.g., tricresyl phosphate (TCP) and the like), phosphorous acid esters,phosphoric acid ester amine salts, phosphorous acid ester amine salts,the like, or combinations thereof; halogen-based extreme pressureagents, such as chlorinated hydrocarbons, the like, or combinationsthereof; organometallic extreme pressure agents, such as thiophosphoricacid salts (e.g., zinc dithiophosphate (ZnDTP) and the like),thiocarbamic acid salts, or combinations thereof; and the like.

The phosphoric acid ester, thiophosphoric acid ester, and amine saltsthereof functions to enhance the lubricating performances, and can beselected from known compounds conventionally employed as extremepressure agents. For example, phosphoric acid esters, a thiophosphoricacid ester, or an amine salt thereof which has an alkyl group, analkenyl group, an alkylaryl group, or an aralkyl group, any of whichcontains approximately 3 to 30 carbon atoms, may be employed.

Examples of the phosphoric acid esters include aliphatic phosphoric acidesters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutylphosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilaurylphosphate, tristearyl phosphate, and trioleyl phosphate; and aromaticphosphoric acid esters such as benzyl phenyl phosphate, allyl diphenylphosphate, triphenyl phosphate, tricresyl phosphate, ethyl diphenylphosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate,ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate,propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate,triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenylphosphate. In an embodiment, the phosphoric acid ester is atrialkylphenyl phosphate.

Examples of the thiophosphoric acid esters include aliphaticthiophosphoric acid esters such as triisopropyl thiophosphate, tributylthiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate,tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearylthiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoricacid esters such as benzyl phenyl thiophosphate, allyl diphenylthiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyldiphenyl thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenylthiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl phenylthiophosphate, propylphenyl diphenyl thiophosphate, dipropylphenylphenyl thiophosphate, triethylphenyl thiophosphate, tripropylphenylthiophosphate, butylphenyl diphenyl thiophosphate, dibutylphenyl phenylthiophosphate, and tributylphenyl thiophosphate. In an embodiment, thethiophosphoric acid ester is a trialkylphenyl thiophosphate.

Also employable are amine salts of the above-mentioned phosphates andthiophosphates. Amine salts of acidic alkyl or aryl esters of thephosphoric acid and thiophosphoric acid are also employable. In anembodiment, the amine salt is an amine salt of trialkylphenyl phosphateor an amine salt of alkyl phosphate.

One or any combination of the compounds selected from the groupconsisting of a phosphoric acid ester, a thiophosphoric acid ester, andan amine salt thereof may be used.

The phosphorus acid ester and/or its amine salt function to enhance thelubricating performance of the composition, and can be selected fromknown compounds conventionally employed as extreme pressure agents. Forexample, the extreme pressure agent can be a phosphorus acid ester or anamine salt thereof, which has an alkyl group, an alkenyl group, analkylaryl group, or an aralkyl group, any of which containsapproximately 3 to 30 carbon atoms.

Examples of phosphorus acid esters that may be used includes aliphaticphosphorus acid esters, such as triisopropyl phosphite, tributylphosphite, ethyl dibutyl phosphite, trihexyl phosphite,tri-2-ethylhexylphosphite, trilauryl phosphite, tristearyl phosphite,and trioleyl phosphite; and aromatic phosphorus acid esters such asbenzyl phenyl phosphite, allyl diphenylphosphite, triphenyl phosphite,tricresyl phosphite, ethyl diphenyl phosphite, tributyl phosphite, ethyldibutyl phosphite, cresyl diphenyl phosphite, dicresyl phenyl phosphite,ethylphenyl diphenyl phosphite, diethylphenyl phenyl phosphite,propylphenyl diphenyl phosphite, dipropylphenyl phenyl phosphite,triethylphenyl phosphite, tripropylphenyl phosphite, butylphenyldiphenyl phosphite, dibutylphenyl phenyl phosphite, and tributylphenylphosphite. Also favorably employed are dilauryl phosphite, dioleylphosphite, dialkyl phosphites, and diphenyl phosphite. In certainembodiments, the phosphorus acid ester is a dialkyl phosphite or atrialkyl phosphite.

The phosphate salt may be derived from a polyamine, such as alkoxylateddiamines, fatty polyamine diamines, alkylenepolyamines, hydroxycontaining polyamines, condensed polyamines arylpolyamines, andheterocyclic polyamines. Examples of these amines include EthoduomeenT/13 and T/20, which are ethylene oxide condensation products ofN-tallowtrimethylenediamine containing 3 and 10 moles of ethylene oxideper mole of diamine, respectively.

In another embodiment, the polyamine is a fatty diamine. The fattydiamine may include mono- or dialkyl, symmetrical or asymmetricalethylene diamines, propane diamines (1,2 or 1,3), and polyamine analogsof the above. Suitable commercial fatty polyamines are Duomeen C(N-coco-1,3-diaminopropane), Duomeen S (N-soya-1,3-diaminopropane),Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen O(N-oleyl-1,3-diaminopropane). “Duomeens” are commercially available fromArmak Chemical Co., Chicago, Ill.

Such alkylenepolyamines include methylenepolyamines, ethylenepolyamines,butylenepolyamines, propylenepolyamines, pentylenepolyamines, etc. Thehigher homologs and related heterocyclic amines, such as piperazines andN-amino alkyl-substituted piperazines, are also included. Specificexamples of such polyamines are ethylenediamine, triethylenetetramine,tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine,pentaethylenehexamine, etc. Higher homologs obtained by condensing twoor more of the above-noted alkyleneamines are similarly useful as aremixtures of two or more of the aforedescribed polyamines.

In one embodiment the polyamine is an ethylenepolyamine. Such polyaminesare described in detail under the heading Ethylene Amines in KirkOthmer's “Encyclopedia of Chemical Technology”, 2nd Edition, Vol. 7,pages 22-37, Interscience Publishers, New York (1965).Ethylenepolyamines can be a complex mixture of polyalkylenepolyamines,including cyclic condensation products.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave, asresidue, what is often termed “polyamine bottoms”. The alkylenepolyaminebottoms can be characterized as having less than 2%, usually less than1% (by weight) material boiling below about 200° C. An exemplary sampleof such ethylene polyamine bottoms obtained from the Dow ChemicalCompany of Freeport, Tex. designated “E-100”. These alkylenepolyaminebottoms include cyclic condensation products, such as piperazine, andhigher analogs of diethylenetriamine, triethylenetetramine and the like.These alkylenepolyamine bottoms can be reacted solely with the acylatingagent or they can be used with other amines, polyamines, or mixturesthereof. Another useful polyamine is a condensation reaction between atleast one hydroxy compound with at least one polyamine reactantcontaining at least one primary or secondary amino group. In anembodiment, the hydroxy compounds are alcohols and amines. Thepolyhydric alcohols are described below. In one embodiment, the hydroxycompounds are polyhydric amines. Polyhydric amines include any of theabove-described monoamines reacted with an alkylene oxide (e.g.,ethylene oxide, propylene oxide, butylene oxide, etc.) having from twoto about 20 carbon atoms, or from two to about four. Examples ofpolyhydric amines include tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, andN,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine. IN an embodiment, thepolyhydric amin is tris(hydroxymethyl)aminomethane (THAM).

Polyamines which react with the polyhydric alcohol or amine to form thecondensation products or condensed amines, are described above. In anembodiment, the polyamine include at least one of triethylenetetramine(TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andmixtures of polyamines, such as the above-described “amine bottoms”.

In some embodiments, the extreme pressure additive or additives includessulphur-based extreme pressure additives, such as dialkyl sulphides,dibenzyl sulphide, dialkyl polysulphides, dibenzyl disulphide, alkylmercaptans, dibenzothiophene, 2,2′-dithiobis(benzothiazole), orcombinations thereof; phosphorus-based extreme pressure additives, suchas trialkyl phosphates, triaryl phosphates, trialkyl phosphonates,trialkyl phosphites, triaryl phosphites, dialkylhydrozine phosphites, orcombinations thereof; and/or phosphorus- and sulphur-based extremepressure additives, such as zinc dialkyldithiophosphates,dialkylthiophosphoric acid, trialkyl thiophosphate esters, acidicthiophosphate esters, trialkyl trithiophosphates, or combinationsthereof. Extreme pressure additives can be used individually or in theform of mixtures, conveniently in an amount within the range from zeroto about 2% by weight of the composition of the present disclosure.

Molybdenum-Containing Compounds (Friction Reducers). Illustrativemolybdenum-containing friction reducers useful in the disclosureinclude, for example, an oil-soluble decomposable organo molybdenumcompound, such as Molyvan™ 855 which is an oil soluble secondarydiarylamine defined as substantially free of active phosphorus andactive sulfur. The Molyvan™ 855 is described in Vanderbilt's MaterialData and Safety Sheet as a organomolybdenum compound having a density of1.04 and viscosity at 100° C. of 47.12 cSt. The organo molybdenumcompounds may be useful because of their superior solubility andeffectiveness.

Another illustrative molybdenum-containing compound is Molyvan™ L, whichis sulfonated oxymolybdenum dialkyldithiophosphate described in U.S.Pat. No. 5,055,174 hereby incorporated by reference.

Molyvan™ A made by R. T. Vanderbilt Company, Inc., New York, N.Y., USA,is also an illustrative molybdenum-containing compound, which containsabout 28.8 wt. % Mo, 31.6 wt. % C, 5.4 wt. % H., and 25.9 wt. % S. Alsouseful are Molyvan™ 855, Molyvan™ 822, Molyvan™ 856, and Molyvan™ 807.

Also useful is Sakura Lube™ 500, which is more soluble Modithiocarbamate containing lubricant additive obtained from Asahi DenkiCorporation and comprised of about 20.2 wt. % Mo, 43.8 wt. % C, 7.4 wt.% H, and 22.4 wt. % S. Sakura LubeTM 300, a low sulfur molybdenumdithiophosphate having a molybdenum to sulfur ratio of 1:1.07, is amolybdenum- containing compound useful in this disclosure.

Also useful is Molyvan™ 807, a mixture of about 50 wt. % molybdenumditridecyldithyocarbonate, and about 50 wt. % of an aromatic oil havinga specific gravity of about 38.4 SUS and containing about 4.6 wt. %molybdenum, also manufactured by R. T. Vanderbilt and marketed as anantioxidant and antiwear additive.

Other sources are molybdenum Mo(Co)₆, and molybdenum octoate,MoO(C₇H₁₅CO₂)₂ containing about 8 wt- % Mo marketed by Aldrich ChemicalCompany, Milwaukee, Wis. and molybdenum naphthenethioctoate marketed byShephard Chemical Company, Cincinnati, Ohio.

Inorganic molybdenum compounds, such as molybdenum sulfide andmolybdenum oxide, are substantially less preferred than the organiccompounds as described in Molyvan™ 855, Molyvan™ 822, Molyvan™ 856, andMolyvan™ 807.

Illustrative molybdenum-containing compounds useful in this disclosureare disclosed, for example, in U.S. Patent Application Publication No.2003/0119682, which is incorporated herein by reference.

Organo molybdenum-nitrogen complexes may also be included in theformulations of the present disclosure. The term “organo molybdenumnitrogen complexes” embraces the organo molybdenum nitrogen complexesdescribed in U.S. Pat. No. 4,889,647. The complexes are reactionproducts of a fatty oil, dithanolamine and a molybdenum source. Specificchemical structures have not been assigned to the complexes. U.S. Pat.No. 4,889,647 reports an infrared spectrum for an exemplary reactionproduct of that disclosure; the spectrum identifies an ester carbonylband at 1740 cm 1 and an amide carbonyl band at 1620 cm 1. The fattyoils are glyceryl esters of higher fatty acids containing at least 12carbon atoms up to 22 carbon atoms or more. The molybdenum source is anoxygen-containing compound such as ammonium molybdates, molybdenumoxides and mixtures.

Other organo molybdenum complexes which can be used in the presentdisclosure are tri nuclear molybdenum sulfur compounds described in EP 1040 115 and WO 99/31113, and the molybdenum complexes described in U.S.Pat. No. 4,978,464.

Although their presence is not required to obtain the benefit of thepresent disclosure, molybdenum-containing additives may be used in anamount of from zero to about 5.0 (e.g., <about 5, ≤ about 4, ≤ about 3,≤ about 2, or ≤ about 1) percent by mass of the composition of thepresent disclosure. For example, the dosage may be up to about 3,000 ppmby mass, such as from about about 100 ppm to about about 2,500 ppm bymass, from about 300 to about 2,000 ppm by mass, or from about 300 toabout 1,500 ppm by mass of molybdenum.

The articles “a” and “an” herein refer to one or to more than one (e.g.at least one) of the grammatical object. Any ranges cited herein areinclusive. The term “about” used throughout is used to describe andaccount for small fluctuations. For instance, “about” may mean thenumeric value may be modified by ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%,±0.3%, ±0.2%, ±0.1% or ±0.05%. All numeric values are modified by theterm “about” whether or not explicitly indicated. Numeric valuesmodified by the term “about” include the specific identified value. Forexample “about 5.0” includes 5.0.

U.S. patents, U.S. patent applications and published U.S. patentapplications discussed herein are hereby incorporated by reference.

Unless otherwise indicated, all parts and percentages are by weight.Weight percent (wt %), if not otherwise indicated, is based on an entirecomposition free of any volatiles.

EXAMPLE 1 Polymer Preparation

An antioxidant diphenyl amine monomer mixture containingN,N-diphenylamine, N,N-di-(p-tert-butylphenyl)amine,N,N-di-(p-tert-octylphenyl)amine, N-(p-tert-butylphenyl)-N-phenylamine,N-(p-tert-octylphenyl)-N-phenylamine andN-(p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine is charged togetherwith n-decane to a 3 L glass reactor connected to a Dean-Stark head witha reflux condenser. The mixture is heated to 135° C. and t-butylperoxideis added dropwise with stirring. The temperature is maintained at 135°C. to 140° C. with stirring and t-butanol is distilled off. Samples areremoved and tested for viscosity. Upon reaching a desired viscosity,unreacted peroxide is removed under reduced pressure, then the mixtureis heated under reduced pressure to remove remaining volatiles. Thediphenyl amine monomer mixture is CAS number 68411-46-1;N-phenyl-benzenamine reaction products with 2,4,4-trimethylpentene.

The monomer mixture exhibits a viscosity of 9.1 cSt (monomer). Polymersor oligomers are prepared having viscosities of 21 cSt (inventive sample1), 81 cSt (inventive sample 2) and 100 cSt (inventive sample 3).Viscosity is kinematic viscosity at 100° C. determined according to ASTMD445.

The viscosity and Mn of the samples can be controlled by, e.g., thelength of the reaction or the feed of the peroxide.

EXAMPLE 2 Bench Testing

Fully formulated oils are prepared containing 81.8% base stock, 16.2%additives and 2%, each by weight, of the samples of Example 1. Allformulated oils exhibit a viscosity at 40° C. of from 52-53 cStaccording to ASTM D445. The samples are tested for total depositsaccording to TEOST MHT 4 test (ASTM D7097), a bench test used toevaluate oil performance relative to forming moderately high temperaturepiston deposits when subjected to high power and temperature operatingconditions. The samples are also tested for total deposits according toTEOST 33C (ASTM D6335), a test that simulates the effect of engineoperating conditions on the oxidation and deposit-forming tendencies ofengine oils, especially in the high temperature turbocharger area. Totaldeposits results (mg) are below.

sample TEOST MHT 4 TEOST 33C monomer 55 36 inventive 1 45 36 inventive 241 33 inventive 3 35 31

Inventive samples are superior regarding deposits formation.

EXAMPLE 3 Engine Testing

The formulated oils containing inventive sample 3 and the monomermixture are tested according to a modified Sequence IIIH engine test.The additives are each added to an engine oil at 2 wt %. The SequenceIIIH Test (ASTM D8111) is a fired-engine, dynamometer lubricant test forevaluating automotive engine oils for certain high-temperatureperformance characteristics, including oil thickening, varnishdeposition and oil consumption. Results are below.

monomer inventive 3 EOT % viscosity increase 432% 68% weighted pistondeposit merits 4.72 5.06 average piston varnish merits 9.61 9.87

EOT % viscosity increase is “end of test” viscosity increase. Theinventive 3 sample provides for outstanding viscosity performance whilemaintaining improved deposits performance. Higher “merits” is better.

EXAMPLE 4 Color

The formulated oils containing inventive sample 3 and the monomermixture exhibit an ASTM D1500 color rating of 4.0 and 3.5, respectively.

EXAMPLE 5

It is demonstrated that m/z ions in the isolated polymers and oligomersshow a correlation to increased performance in a VIT test.

The table below shows that the m/z ion counts at 838, 984 and 911Daltons are significantly higher than the #4 residue which has a lowerVIT result. The higher the VIT value, the better the antioxidant

Sample VIT (h to pvisc 150) 838 894 911 Reference 470 0 0 0 Sample 1 830296 225 65 Sample 2 797 386 179 65 Sample 3 533 49 65 8

FIG. 1 shows a trend that VIT performance is better when there is agreater amount of dimers and trimers as compared to the amount of higherpolymers (4+) in conjunction with the LC/MS data that yields the 838 and894 (which corresponds to 837 and 893 Daltons)

EXAMPLE 6

A polymeric composition of the present disclosure is included as acomponent in a grease formulation as shown below.

Formulation Details (wt %) Base Stocks 71.5-73% 71.5-73% 71.5-73%Thickener   7-8.5   7-8.5   7-8.5 Additives 13.37 13.37 13.37 (Standard)IRGANOX L57 1.00 2.00 0.00 Inventive 3 0.00 0.00 1.00 Total 100 100 100Testing Results ASTM D445 - Kinematic Viscosity 220.0 220.0 220.0 at 40°C. (cSt) ASTM D217 - Penetration, Worked 287.0 287.0 294.0 (0.1 mm) ASTMD5483 PDSC of Greases 23 N/A 17.3 (Isothermal at 210 C.) ASTM D942 -Pressure Vessel 1.1 N/A 2.4 Oxidation Test @ 100 hrs (psi drop) ASTMD942 - Pressure Vessel 8 N/A 10.4 Oxidation Test @ 100 hrs (psi drop)DIN 51821 FAG FE9 FE9 84.0 135.0 A/1500/6000 @ 140 C. (B50, hours)

All of the formulations in the above Table are Lithium complex (thicknertype) greases, with ISO Viscosity grades of 220 and an NLGI consistencygrade of 2. Common grease thickener types are simple lithium soap,lithium complex soap, polyurea, calcium sulfonate, aluminum soap,calcium soap, mixed aluminum/calcium, clay and polymer thickened.Greases contain, e.g., 70-80% basestock, 0.1-20% thickener, and 0-20%additives. The data demonstrates that the inventive example treated at1% has the same oxidative performance as the commercial example treatedat 1% in grease bench oxidation tests (ASTM D5483 and D942). However,when the same greases were tested in the DIN 51821 FAG FE9 test (rigtest-high temperature bearing performance of a grease) the grease withthe inventive example demonstrated superior performance compare to thegrease that contained 1% commercial example and the grease thatcontained 2% of the commercial example. This is unexpected given theequivalent performance in the bench oxidation testing. According to theabove data, the inventive polymer composition can be utilized in thepreparation of a grease to improve high temperature bearing performance.

EXAMPLE 7

A polymeric composition of the present invention is included as acomponent in an industrial oil formulation as shown below.

Base Stocks 97.94 97.94 97.94 97.94 97.94 97.94 Additives 13.37 13.3713.37 13.37 13.37 13.37 (Standard) 1.00 0.00 0.00 0.70 0.00 0.00 IRGANOXL57 Inventive 3 0.00 1.00 0.00 0.00 0.00 0.00 Inventive 7 0.00 0.00 1.000.00 0.70 0.00 Inventive 8 0.00 0.00 0.00 0.00 0.00 0.70 Total 100 100100 100 100 100 Testing Results ASTM 30.4 30.8 31.1 30.6 30.9 31Viscosity D445-Kinematic at 40° C. (cSt) ASTM D2272- 1974.0 2119.0 20362207 2611 2027 RPVOT at 150 C. (min) High Pressure 222.2 193.1 236.5847.3 94.03 20 Differential Scanning Calorimetry (min)

EXAMPLE 8

A polymeric composition of the present invention is included as acomponent in a passenger vehicle lubricant formulation as shown below.

Formulation Details (wt %) Base Stocks 81.76 81.76 81.76 81.76 81.7681.76 81.76 Additives 16.24 16.24 16.24 16.24 16.24 16.24 16.24(Standard) IRGANOX L57 2.00 0.00 0.00 0.00 0.00 0.00 0.00 Inventive 20.00 2.00 0.00 0.00 0.00 0.00 0.00 Inventive 1 0.00 0.00 2.00 0.00 0.000.00 0.00 Inventive 3 0.00 0.00 0.00 2.00 0.00 0.00 0.00 Inventive 70.00 0.00 0.00 0.00 2.00 0.00 0.00 Inventive 8 0.00 0.00 0.00 0.00 0.002.00 0.00 Inventive 9 0.00 0.00 0.00 0.00 0.00 0.00 2.00 Total 100 100100 100 100 100 100 Testing Results ASTM D445-Kinematic 51.9 52.6 53.253.2 53.7 53.4 54.4 Viscosity at 40° C. (cSt) ASTM D7097-TEOST MHT4 55.045.2 41.0 34.8 — — — (Total deposits, mg) ASTM D6335-TEOST 33 C. 35.836.2 33.0 30.8 — — — (Total deposits, mg) ASTM D1500-Color 3.5 TBD TBD4.0 5.5 6 5 ASTM D8111-Sequence IIIH, 432% — — 68% 114.6 240.3 172.2 EOT% Viscosity increase ASTM D8111-Sequence IIIH, 4.72 — — 5.06 5.15 4.274.87 Weighted Piston Deposit Merits ASTM D8111-Sequence IIIH, 9.61 — —9.87 9.68 9.47 9.68 Average Piston Varnish Merits

EXAMPLE 9

A polymeric composition of the present invention is included as acomponent in a commercial vehicle lubricant formulation as shown below.

Formulation Details (wt %) Base Stocks 80.38 80.38 Additives 18.22 18.22(Standard) IRGANOX L57 1.40 0.00 Inventive 3 0.00 1.40 Total 100 100Testing Results ASTM D445 - Kinematic Viscosity 56.7 54.4 at 40° C.(cSt) ASTM D8048 - Volvo T-13, 70.6 78.9 EOT % Viscosity Increase ASTMD8048 - Volvo T-13, 148.0 127.0 IR Peak Increase

Legend for the above Examples

Inventive Antioxidant Polymers# Inventive 1 Lower molecular weightoligomeric material Inventive 2 Lower molecular weight oligomericmaterial Inventive 3 Lower molecular weight oligomeric materialInventive 4 Oligomers no diluent Inventive 5 Oligomers no diluentInventive 6 Isolated Substance, OECD polymer 75% Mn > 1000 Inventive 775% Mn > 1000 plus L57 as diluent Inventive 8 75% Mn > 1000 plus L57 asdiluent Inventive 9 75% Mn > 1000 plus L57 as diluent

1. A lubricating oil composition comprising a base oil; and from about0.01 wt % to about 20 wt %, based on the total weight of the lubricatingoil composition, of an antioxidant polymer composition comprising repeatunits of diphenylamine monomers of formula I

wherein R is H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,—C(O)C₁-C₁₈ alkyl, —C(O)aryl and R₁, R₂, R₃ and R₄ are eachindependently H or a linear or branched C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,C₁-C₁₈ alkylamino, C₁-C₁₈ dialkylamino, C₁-C₁₈ alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl or C₇-C₂₁ aralkyl and wherein the number averagemolecular weight (Mn) of the polymer composition is from about 350 g/molto about 5000 g/mol.
 2. The lubricating oil composition according toclaim 1, comprising one or more components selected from the groupconsisting of other antioxidants, antiwear additives, viscosity indeximprovers, detergents, dispersants, pour point depressants, corrosioninhibitors, metal deactivators, seal compatibility additives, antifoamagents, inhibitors, antirust additives, and friction modifiers.
 3. Thelubricating oil composition according to claim 1, wherein the Mn of thepolymer composition is from about 400 g/mol to about 5000 g/mol.
 4. Thelubricating oil composition according to claim 1, wherein R₁, R₂, R₃ andR₄ are each independently H or a linear or branched C₄-C₁₀ alkyl.
 5. Thelubricating oil composition according to claim 1, wherein R is H.
 6. Thelubricating oil composition according to claim 1, wherein the polymercomposition further comprises one or more monomers selected from thegroup consisting of other diphenylamines, phenothiazines, phenoxazines,aminodiphenylamines, methylenedianiline, toluenediamine, aminophenols,alkylphenols, thiophenols, phenylenediamines, quinolines, phenylpyridinediamines, pyridinepyrimidinediamines andphenylpyrimidinediamines.
 7. The lubricating oil composition accordingto claim 1, wherein the polymer composition comprises from about 10 mol% to about 99 mol % diphenylamine monomers.
 8. The lubricating oilcomposition according to claim 1, wherein the polymer compositioncomprises <70 wt % residual monomers of formula I.
 9. The lubricatingoil composition according to claim 1, wherein the polymer compositioncomprises from about 1 wt % to about 70 wt % residual monomers offormula I, based on the total weight of the polymer composition.
 10. Thelubricating oil composition according to claim 1, wherein the viscosityof the polymer composition is from about 20 cSt to about 600 cSt. 11.The lubricating oil composition according to claim 1, wherein thepolymer composition is a solid.
 12. The lubricating oil compositionaccording to claim 1, wherein the base oil comprises a natural oil or asynthetic oil.
 13. The lubricating oil composition according to claim 1,wherein the base oil comprises a mineral oil, a polyalphaolefin, analkyl naphthalene or a gas-to-liquid base stock.
 14. The lubricating oilcomposition according to claim 1, comprising from about 50 wt % to about90 wt % base oil, based on the total weight of the lubricating oilcomposition.
 15. The lubricating oil composition according to claim 1,which exhibits color of <about 5.5according to ASTM D1500.
 16. Thelubricating oil composition according to claim 1, comprising anantioxidant combination of the polymer composition and one or moreantioxidants selected from the group consisting of further aminic andphenolic antioxidants.
 17. The lubricating oil composition according toclaim 1, comprising an antioxidant combination of the polymercomposition and one or more further compounds selected from the groupconsisting of N,N-di-(p-tert-butylphenyl)amine,N,N-di-(p-tert-octylphenyl)amine, N-(p-tert-butylphenyl)-N-phenylamine,N-(p-tert-octylphenyl)-N-phenylamine andN-(p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine,bis-nonylphenyldiphenylamine, N-(tert-C₁-C₂₀alkylphenyl)-1-naphthylamineand 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid octyl ester.
 18. Alubricating oil composition comprising a base oil; and from about 0.01wt % to about 20 wt %, based on the total weight of the lubricating oilcomposition, of a polymer composition comprising repeat units ofdiphenylamine monomers of formula I

wherein R is H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,—C(O)C₁-C₁₈ alkyl, —C(O)aryl and R₁, R₂, R₃ and R₄ are eachindependently H or a linear or branched C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,C₁-C₁₈ alkylamino, C₁-C₁₈ dialkylamino, C₁-C₁₈ alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl or C₇-C₂₁ aralkyl, and wherein the polymercomposition comprises ≤70 wt % residual monomers of formula I.
 19. Thelubrication oil composition according to claim 18, wherein the polymercomposition comprises ≤30 wt % residual monomers of formula I.
 20. Thelubricating oil composition according to claim 18, wherein the polymercomposition comprises from about 1 wt % to about 70 wt % residualmonomers of formula I, based on the total weight of the polymercomposition.
 21. A method of reducing extending an oil drain interval,the method comprising adding to the engine the lubricating oilcomposition of claim
 1. 22. A method of improving oxidative stability ofa lubricating oil in an engine, the method comprising adding to theengine the lubricating oil composition of claim
 1. 23. A process ofproviding a lubricating oil composition oxidative stability, depositscontrol and viscosity control, the process comprising incorporating apolymer composition comprising repeat units of diphenylamine monomers offormula I

wherein R is H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,—C(O)C₁-C₁₈ alkyl, —C(O)aryl and R₁, R₂, R₃ and R₄ are eachindependently H or a linear or branched C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,C₁-C₁₈ alkylamino, C₁-C₁₈ dialkylamino, C₁-C₁₈ alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl or C₇-C₂₁ aralkyl and wherein the number averagemolecular weight (Mn) of the polymer composition is from about 350 g/molto about 5000 g/mol; into a base oil, wherein the lubricating oilcomposition comprises from about 0.01 wt % to about 20 wt %, based onthe total weight of the lubricating oil composition, of the polymercomposition.
 24. The lubricating oil composition of claim 1, wherein thepolymer composition is an oligomer composition.
 25. The lubricating oilcomposition of claim 18, wherein the polymer composition is an oligomercomposition.